Southern Ocean drives multidecadal atmospheric CO2 rise during Heinrich Stadials.

The last glacial period was punctuated by cold intervals in the North Atlantic region that culminated in extensive iceberg discharge events. These cold intervals, known as Heinrich Stadials, are associated with abrupt climate shifts worldwide. Here, we present CO2 measurements from the West Antarctic Ice Sheet Divide ice core across Heinrich Stadials 2 to 5 at decadal-scale resolution. Our results reveal multi-decadal-scale jumps in atmospheric CO2 concentrations within each Heinrich Stadial. The largest magnitude of change (14.0 ± 0.8 ppm within 55 ± 10 y) occurred during Heinrich Stadial 4. Abrupt rises in atmospheric CO2 are concurrent with jumps in atmospheric CH4 and abrupt changes in the water isotopologs in multiple Antarctic ice cores, the latter of which suggest rapid warming of both Antarctica and Southern Ocean vapor source regions. The synchroneity of these rapid shifts points to wind-driven upwelling of relatively warm, carbon-rich waters in the Southern Ocean, likely linked to a poleward intensification of the Southern Hemisphere westerly winds. Using an isotope-enabled atmospheric circulation model, we show that observed changes in Antarctic water isotopologs can be explained by abrupt and widespread Southern Ocean warming. Our work presents evidence for a multi-decadal- to century-scale response of the Southern Ocean to changes in atmospheric circulation, demonstrating the potential for dynamic changes in Southern Ocean biogeochemistry and circulation on human timescales. Furthermore, it suggests that anthropogenic CO2 uptake in the Southern Ocean may weaken with poleward strengthening westerlies today and into the future.

Single Particle Characterization and Total Elemental Concentration Measurements in Polar Ice Using Continuous Flow Analysis-Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Continuous flow analysis (CFA) has become widely used for the measurement of aerosol-derived impurities in ice-core samples, resulting in high-resolution data sets of past aerosol deposition. Here, we present first results from coupling an inductively coupled plasma time-of-flight mass spectrometer (TOFMS) to a traditional CFA system. This setup enables the measurement of exactly coregistered elemental concentrations over the full mass range without degradation of sensitivity with an increasing number of analytes. The resulting total elemental concentration records have similar or better resolution than the established spectrophotometric methods. The unique capability of a TOFMS to measure fast transient signals and to still cover the full mass range furthermore enables the detection of the ionization of individual insoluble particles entering the plasma. The resulting mass spectra of the particles can be used to investigate the relative elemental composition of the mineral dust particles preserved in ice. The presented analysis of iron-bearing particles indicates that most of the particulate iron in Greenland ice is associated with Mg and Al and is likely part of clay minerals such as illite.

Earth's radiative imbalance from the Last Glacial Maximum to the present.

The energy imbalance at the top of the atmosphere determines the temporal evolution of the global climate, and vice versa changes in the climate system can alter the planetary energy fluxes. This interplay is fundamental to our understanding of Earth's heat budget and the climate system. However, even today, the direct measurement of global radiative fluxes is difficult, such that most assessments are based on changes in the total energy content of the climate system. We apply the same approach to estimate the long-term evolution of Earth's radiative imbalance in the past. New measurements of noble gas-derived mean ocean temperature from the European Project for Ice Coring in Antarctica Dome C ice core covering the last 40,000 y, combined with recent results from the West Antarctic Ice Sheet Divide ice core and the sea-level record, allow us to quantitatively reconstruct the history of the climate system energy budget. The temporal derivative of this quantity must be equal to the planetary radiative imbalance. During the deglaciation, a positive imbalance of typically +0.2 W⋅m-2 is maintained for ∼10,000 y, however, with two distinct peaks that reach up to 0.4 W⋅m-2 during times of substantially reduced Atlantic Meridional Overturning Circulation. We conclude that these peaks are related to net changes in ocean heat uptake, likely due to rapid changes in North Atlantic deep-water formation and their impact on the global radiative balance, while changes in cloud coverage, albeit uncertain, may also factor into the picture.

Industrial-era decline in subarctic Atlantic productivity.

Marine phytoplankton have a crucial role in the modulation of marine-based food webs1, fishery yields2 and the global drawdown of atmospheric carbon dioxide3. However, owing to sparse measurements before satellite monitoring in the twenty-first century, the long-term response of planktonic stocks to climate forcing is unknown. Here, using a continuous, multi-century record of subarctic Atlantic marine productivity, we show that a marked 10 ± 7% decline in net primary productivity has occurred across this highly productive ocean basin over the past two centuries. We support this conclusion by the application of a marine-productivity proxy, established using the signal of the planktonic-derived aerosol methanesulfonic acid, which is commonly identified across an array of Greenlandic ice cores. Using contemporaneous satellite-era observations, we demonstrate the use of this signal as a robust and high-resolution proxy for past variations in spatially integrated marine productivity. We show that the initiation of declining subarctic Atlantic productivity broadly coincides with the onset of Arctic surface warming4, and that productivity strongly covaries with regional sea-surface temperatures and basin-wide gyre circulation strength over recent decades. Taken together, our results suggest that the decline in industrial-era productivity may be evidence of the predicted5 collapse of northern Atlantic planktonic stocks in response to a weakened Atlantic Meridional Overturning Circulation6-8. Continued weakening of this Atlantic Meridional Overturning Circulation, as projected for the twenty-first century9,10, may therefore result in further productivity declines across this globally relevant region.

Fe2+ in ice cores as a new potential proxy to detect past volcanic eruptions.

Volcanic eruptions are widely used in ice core science to date or synchronize ice cores. Volcanoes emit large amounts of SO2 that is subsequently converted in the atmosphere into sulfuric acid/sulphate. Its discrete and continuous quantification is currently used to determine the ice layers impacted by volcanic emissions, but available high-resolution sulphate quantification methods in ice core (Continuous Flow Analysis (CFA)) struggle with insufficient sensitivity. Here, we present a new high-resolution CFA chemiluminescence method for the continuous determination of Fe2+ species in ice cores that shows clear Fe2+ peaks concurrent with volcanic sulphate peaks in the ice core record. The method, applied on a Greenland ice core, correctly identifies all volcanic eruptions from between 1588 to 1611 and from 1777 to 1850. The method has a detection limit of ∽5 pg g-1 and a quadratic polynomial calibration range of up to at least 1760 pg g-1. Our results show that Fe2+ is a suitable proxy for identifying past volcanic events.

High-resolution isotopic evidence for a potential Saharan provenance of Greenland glacial dust.

Dust concentrations in Greenland ice show pronounced glacial/interglacial variations with almost two orders of magnitude increase during the Last Glacial Maximum. Greenland glacial dust was previously sourced to two East Asian deserts: the Taklimakan and Gobi deserts. Here we report the first high-resolution Pb and Sr isotopic evidence for a significant Saharan dust influence in Greenland during the last glacial period, back to ~31 kyr ago, from the Greenland NEEM ice core. We find that during Greenland Stadials 3-5.1 (~31 to 23 kyr ago), the primary dust provenance was East Asia, as previously proposed. Subsequently, the Saharan isotopic signals emerge during Greenland Stadials 2.1a-2.1c (~22.6 to 14.7 kyr ago) and from the late Bølling-Allerød to the Younger Dryas periods (~13.6 to 12 kyr ago), coincident with increased aridity in the Sahara and efficient northward transport of dust during these cold periods. A mixing isotopic model proposes the Sahara as an important source, accounting for contribution to Greenland glacial dust of up to 50%, particularly during Greenland Stadial 2.1b and the late Bølling-Allerød to the Younger Dryas periods. Our findings provide new insights into climate-related dust provenance changes and essential paleoclimatic constraints on dust-climate feedbacks in northern high latitudes.

Glacial/interglacial wetland, biomass burning, and geologic methane emissions constrained by dual stable isotopic CH4 ice core records.

Atmospheric methane (CH4) records reconstructed from polar ice cores represent an integrated view on processes predominantly taking place in the terrestrial biogeosphere. Here, we present dual stable isotopic methane records [δ13CH4 and δD(CH4)] from four Antarctic ice cores, which provide improved constraints on past changes in natural methane sources. Our isotope data show that tropical wetlands and seasonally inundated floodplains are most likely the controlling sources of atmospheric methane variations for the current and two older interglacials and their preceding glacial maxima. The changes in these sources are steered by variations in temperature, precipitation, and the water table as modulated by insolation, (local) sea level, and monsoon intensity. Based on our δD(CH4) constraint, it seems that geologic emissions of methane may play a steady but only minor role in atmospheric CH4 changes and that the glacial budget is not dominated by these sources. Superimposed on the glacial/interglacial variations is a marked difference in both isotope records, with systematically higher values during the last 25,000 y compared with older time periods. This shift cannot be explained by climatic changes. Rather, our isotopic methane budget points to a marked increase in fire activity, possibly caused by biome changes and accumulation of fuel related to the late Pleistocene megafauna extinction, which took place in the course of the last glacial.

Atmospheric impacts of the strongest known solar particle storm of 775 AD.

Sporadic solar energetic particle (SEP) events affect the Earth's atmosphere and environment, in particular leading to depletion of the protective ozone layer in the Earth's atmosphere, and pose potential technological and even life hazards. The greatest SEP storm known for the last 11 millennia (the Holocene) occurred in 774-775 AD, serving as a likely worst-case scenario being 40-50 times stronger than any directly observed one. Here we present a systematic analysis of the impact such an extreme event can have on the Earth's atmosphere. Using state-of-the-art cosmic ray cascade and chemistry-climate models, we successfully reproduce the observed variability of cosmogenic isotope 10Be, around 775 AD, in four ice cores from Greenland and Antarctica, thereby validating the models in the assessment of this event. We add to prior conclusions that any nitrate deposition signal from SEP events remains too weak to be detected in ice cores by showing that, even for such an extreme solar storm and sub-annual data resolution, the nitrate deposition signal is indistinguishable from the seasonal cycle. We show that such a severe event is able to perturb the polar stratosphere for at least one year, leading to regional changes in the surface temperature during northern hemisphere winters.

Isotopic constraints on marine and terrestrial N2O emissions during the last deglaciation.

Nitrous oxide (N2O) is an important greenhouse gas and ozone-depleting substance that has anthropogenic as well as natural marine and terrestrial sources. The tropospheric N2O concentrations have varied substantially in the past in concert with changing climate on glacial-interglacial and millennial timescales. It is not well understood, however, how N2O emissions from marine and terrestrial sources change in response to varying environmental conditions. The distinct isotopic compositions of marine and terrestrial N2O sources can help disentangle the relative changes in marine and terrestrial N2O emissions during past climate variations. Here we present N2O concentration and isotopic data for the last deglaciation, from 16,000 to 10,000 years before present, retrieved from air bubbles trapped in polar ice at Taylor Glacier, Antarctica. With the help of our data and a box model of the N2O cycle, we find a 30 per cent increase in total N2O emissions from the late glacial to the interglacial, with terrestrial and marine emissions contributing equally to the overall increase and generally evolving in parallel over the last deglaciation, even though there is no a priori connection between the drivers of the two sources. However, we find that terrestrial emissions dominated on centennial timescales, consistent with a state-of-the-art dynamic global vegetation and land surface process model that suggests that during the last deglaciation emission changes were strongly influenced by temperature and precipitation patterns over land surfaces. The results improve our understanding of the drivers of natural N2O emissions and are consistent with the idea that natural N2O emissions will probably increase in response to anthropogenic warming.

Continuous flow analysis of labile iron in ice-cores.

The important active and passive role of mineral dust aerosol in the climate and the global carbon cycle over the last glacial/interglacial cycles has been recognized. However, little data on the most important aeolian dust-derived biological micronutrient, iron (Fe), has so far been available from ice-cores from Greenland or Antarctica. Furthermore, Fe deposition reconstructions derived from the palaeoproxies particulate dust and calcium differ significantly from the Fe flux data available. The ability to measure high temporal resolution Fe data in polar ice-cores is crucial for the study of the timing and magnitude of relationships between geochemical events and biological responses in the open ocean. This work adapts an existing flow injection analysis (FIA) methodology for low-level trace Fe determinations with an existing glaciochemical analysis system, continuous flow analysis (CFA) of ice-cores. Fe-induced oxidation of N,N'-dimethyl-p-pheylenediamine (DPD) is used to quantify the biologically more important and easily leachable Fe fraction released in a controlled digestion step at pH ~1.0. The developed method was successfully applied to the determination of labile Fe in ice-core samples collected from the Antarctic Byrd ice-core and the Greenland Ice-Core Project (GRIP) ice-core.

Mode change of millennial CO2 variability during the last glacial cycle associated with a bipolar marine carbon seesaw.

Important elements of natural climate variations during the last ice age are abrupt temperature increases over Greenland and related warming and cooling periods over Antarctica. Records from Antarctic ice cores have shown that the global carbon cycle also plays a role in these changes. The available data shows that atmospheric CO(2) follows closely temperatures reconstructed from Antarctic ice cores during these variations. Here, we present new high-resolution CO(2) data from Antarctic ice cores, which cover the period between 115,000 and 38,000 y before present. Our measurements show that also smaller Antarctic warming events have an imprint in CO(2) concentrations. Moreover, they indicate that during Marine Isotope Stage (MIS) 5, the peak of millennial CO(2) variations lags the onset of Dansgaard/Oeschger warmings by 250 ± 190 y. During MIS 3, this lag increases significantly to 870 ± 90 y. Considerations of the ocean circulation suggest that the millennial variability associated with the Atlantic Meridional Overturning Circulation (AMOC) undergoes a mode change from MIS 5 to MIS 4 and 3. Ocean carbon inventory estimates imply that during MIS 3 additional carbon is derived from an extended mass of carbon-enriched Antarctic Bottom Water. The absence of such a carbon-enriched water mass in the North Atlantic during MIS 5 can explain the smaller amount of carbon released to the atmosphere after the Antarctic temperature maximum and, hence, the shorter lag. Our new data provides further constraints for transient coupled carbon cycle-climate simulations during the entire last glacial cycle.

Effects of MRI scan acceleration on brain volume measurement consistency.

PURPOSE: To evaluate the effects of recent advances in magnetic resonance imaging (MRI) radiofrequency (RF) coil and parallel imaging technology on brain volume measurement consistency. MATERIALS AND METHODS: In all, 103 whole-brain MRI volumes were acquired at a clinical 3T MRI, equipped with a 12- and 32-channel head coil, using the T1-weighted protocol as employed in the Alzheimer's Disease Neuroimaging Initiative study with parallel imaging accelerations ranging from 1 to 5. An experienced reader performed qualitative ratings of the images. For quantitative analysis, differences in composite width (CW, a measure of image similarity) and boundary shift integral (BSI, a measure of whole-brain atrophy) were calculated. RESULTS: Intra- and intersession comparisons of CW and BSI measures from scans with equal acceleration demonstrated excellent scan-rescan accuracy, even at the highest acceleration applied. Pairs-of-scans acquired with different accelerations exhibited poor scan-rescan consistency only when differences in the acceleration factor were maximized. A change in the coil hardware between compared scans was found to bias the BSI measure. CONCLUSION: The most important findings are that the accelerated acquisitions appear to be compatible with the assessment of high-quality quantitative information and that for highest scan-rescan accuracy in serial scans the acquisition protocol should be kept as consistent as possible over time.

9,400 years of cosmic radiation and solar activity from ice cores and tree rings.

Understanding the temporal variation of cosmic radiation and solar activity during the Holocene is essential for studies of the solar-terrestrial relationship. Cosmic-ray produced radionuclides, such as (10)Be and (14)C which are stored in polar ice cores and tree rings, offer the unique opportunity to reconstruct the history of cosmic radiation and solar activity over many millennia. Although records from different archives basically agree, they also show some deviations during certain periods. So far most reconstructions were based on only one single radionuclide record, which makes detection and correction of these deviations impossible. Here we combine different (10)Be ice core records from Greenland and Antarctica with the global (14)C tree ring record using principal component analysis. This approach is only possible due to a new high-resolution (10)Be record from Dronning Maud Land obtained within the European Project for Ice Coring in Antarctica in Antarctica. The new cosmic radiation record enables us to derive total solar irradiance, which is then used as a proxy of solar activity to identify the solar imprint in an Asian climate record. Though generally the agreement between solar forcing and Asian climate is good, there are also periods without any coherence, pointing to other forcings like volcanoes and greenhouse gases and their corresponding feedbacks. The newly derived records have the potential to improve our understanding of the solar dynamics and to quantify the solar influence on climate.

Carbon isotope constraints on the deglacial CO2 rise from ice cores.

The stable carbon isotope ratio of atmospheric CO(2) (δ(13)C(atm)) is a key parameter in deciphering past carbon cycle changes. Here we present δ(13)C(atm) data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in δ(13)C(atm) during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the δ(13)C(atm) evolution. During the Last Glacial Maximum, δ(13)C(atm) and atmospheric CO(2) concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.

Hydrogen isotopes preclude marine hydrate CH4 emissions at the onset of Dansgaard-Oeschger events.

The causes of past changes in the global methane cycle and especially the role of marine methane hydrate (clathrate) destabilization events are a matter of debate. Here we present evidence from the North Greenland Ice Core Project ice core based on the hydrogen isotopic composition of methane [deltaD(CH4)] that clathrates did not cause atmospheric methane concentration to rise at the onset of Dansgaard-Oeschger (DO) events 7 and 8. Box modeling supports boreal wetland emissions as the most likely explanation for the interstadial increase. Moreover, our data show that deltaD(CH4) dropped 500 years before the onset of DO 8, with CH4 concentration rising only slightly. This can be explained by an early climate response of boreal wetlands, which carry the strongly depleted isotopic signature of high-latitude precipitation at that time.

A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision deltaD measurements of atmospheric methane extracted from ice cores.

Air enclosures in polar ice cores represent the only direct paleoatmospheric archive. Analysis of the entrapped air provides clues to the climate system of the past in decadal to centennial resolution. A wealth of information has been gained from measurements of concentrations of greenhouse gases; however, little is known about their isotopic composition. In particular, stable isotopologues (deltaD and delta(13)C) of methane (CH(4)) record valuable information on its global cycle as the different sources exhibit distinct carbon and hydrogen isotopic composition. However, CH(4) isotope analysis is limited by the large sample size required and the demanding analysis as high precision is required. Here we present a highly automated, high-precision online gas chromatography/pyrolysis/isotope ratio monitoring mass spectrometry (GC/P/irmMS) technique for the analysis of deltaD(CH(4)). It includes gas extraction from ice, preconcentration, gas chromatographic separation and pyrolysis of CH(4) from roughly 500 g of ice with CH(4) concentrations as low as 350 ppbv. Ice samples with approximately 40 mL air and only approximately 1 nmol CH(4) can be measured with a precision of 3.4 per thousand. The precision for 65 mL air samples with recent atmospheric concentration is 1.5 per thousand. The CH(4) concentration can be obtained along with isotope data which is crucial for reporting ice core data on matched time scales and enables us to detect flaws in the measurement procedure. Custom-made script-based processing of MS raw and peak data enhance the system's performance with respect to stability, peak size dependency, hence precision and accuracy and last but not least time requirement.

Sulfate spikes in the deep layers of EPICA-Dome C ice core: evidence of glaciological artifacts.

A detailed ionic component record was performed on EPICA Dome C ice core (East Antarctica) to a depth of 3190 m using Ion Chromatography and Fast Ion Chromatography (FIC). At depths greater than 2800 m, the sulfate profile shows intense, sharp spikes which are not expected due to the smoothing of sulfate peaks by diffusion processes. Moreover, these spikes show an "anomalous" chemical composition (e.g., unusually low acidity, high Mg(2+) concentration and high Mg(2+)/Ca(2+) ratio). These peaks and the surrounding layers also exhibit good Mg(2+) vs SO(4)(2-) and Cl(-) vs Na(+) correlations through both glacial and interglacial periods. Furthermore, the high-resolution analysis of two horizontally contiguous ice sections showed that some fraction of the impurities are characterized by a heterogeneous distribution. Altogether, these results suggest the occurrence of long-term postdepositional processes involving a rearrangement of impurities via migration in the vein network, characterized by sulfuric acidity and leading to the formation of soluble particles of magnesium sulfate salts, along with ionic association of ions in the liquid films along boundaries. This evidence should be taken into consideration when inferring information on for rapid climatic and environmental changes from ice core chemical records at great depths. At Dome C, the depth threshold was found to be 2800 m.

Stable isotope constraints on Holocene carbon cycle changes from an Antarctic ice core.

Reconstructions of atmospheric CO(2) concentrations based on Antarctic ice cores reveal significant changes during the Holocene epoch, but the processes responsible for these changes in CO(2) concentrations have not been unambiguously identified. Distinct characteristics in the carbon isotope signatures of the major carbon reservoirs (ocean, biosphere, sediments and atmosphere) constrain variations in the CO(2) fluxes between those reservoirs. Here we present a highly resolved atmospheric delta(13)C record for the past 11,000 years from measurements on atmospheric CO(2) trapped in an Antarctic ice core. From mass-balance inverse model calculations performed with a simplified carbon cycle model, we show that the decrease in atmospheric CO(2) of about 5 parts per million by volume (p.p.m.v.). The increase in delta(13)C of about 0.25 per thousand during the early Holocene is most probably the result of a combination of carbon uptake of about 290 gigatonnes of carbon by the land biosphere and carbon release from the ocean in response to carbonate compensation of the terrestrial uptake during the termination of the last ice age. The 20 p.p.m.v. increase of atmospheric CO(2) and the small decrease in delta(13)C of about 0.05 per thousand during the later Holocene can mostly be explained by contributions from carbonate compensation of earlier land-biosphere uptake and coral reef formation, with only a minor contribution from a small decrease of the land-biosphere carbon inventory.

A new method for high-resolution methane measurements on polar ice cores using continuous flow analysis.

Methane (CH4) is the second most important anthropogenic greenhouse gas in the atmosphere. Rapid variations of the CH4 concentration, as frequently registered, for example, during the last ice age, have been used as reliable time markers for the definition of a common time scale of polar ice cores. In addition, these variations indicate changes in the sources of methane primarily associated with the presence of wetlands. In order to determine the exact time evolution of such fast concentration changes, CH4 measurements of the highest resolution in the ice core archive are required. Here, we present a new, semicontinuous and field-deployable CH4 detection method, which was incorporated in a continuous flow analysis (CFA) system. In CFA, samples cut along the axis of an ice core are melted at a melt speed of typically 3.5 cm/min. The air from bubbles in the ice core is extracted continuously from the meltwater and forwarded to a gas chromatograph (GC) for high-resolution CH4 measurements. The GC performs a measurement every 3.5 min, hence, a depth resolution of 15 cm is achieved atthe chosen melt rate. An even higher resolution is not necessary due to the low pass filtering of air in ice cores caused by the slow bubble enclosure process and the diffusion of air in firn. Reproducibility of the new method is 3%, thus, for a typical CH4 concentration of 500 ppb during an ice age, this corresponds to an absolute precision of 15 ppb, comparable to traditional analyses on discrete samples. Results of CFA-CH4 measurements on the ice core from Talos Dome (Antarctica) illustrate the much higher temporal resolution of our method compared with established melt-refreeze CH4 measurements and demonstrate the feasibility of the new method.

A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision delta13C measurements of atmospheric methane extracted from ice core samples.

Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of delta13CH4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of approximately 200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 +/- 40 years) show a delta13C(VPDB) of -49.54 +/- 0.13 per thousand and Antarctic samples (1530 +/- 25 years) show a delta13C(VPDB) of -48.00 +/- 0.12 per thousand in good agreement with published data.