Alvaro Fernandez

Blank Corrections for Ramped Pyrolysis Radiocarbon Dating of Sedimentary and Soil Organic Carbon

Ramped pyrolysis (RP) targets distinct components of soil and sedimentary organic carbon based on their thermochemical stabilities and allows the determination of the full spectrum of radiocarbon ((14)C) ages present in a soil or sediment sample. Extending the method into realms where more precise ages are needed or where smaller samples need to be measured involves better understanding of the blank contamination associated with the method. Here, we use a compiled data set of RP measurements of samples of known age to evaluate the mass of the carbon blank and its associated (14)C signature, and to assess the performance of the RP system. We estimate blank contamination during RP using two methods, the modern-dead and the isotope dilution method. Our results indicate that during one complete RP run samples are contaminated by 8.8 ± 4.4 μg (time-dependent) of modern carbon (MC, fM ∼ 1) and 4.1 ± 5.5 μg (time-independent) of dead carbon (DC, fM ∼ 0). We find that the modern-dead method provides more accurate estimates of uncertainties in blank contamination; therefore, the isotope dilution method should be used with caution when the variability of the blank is high. Additionally, we show that RP can routinely produce accurate (14)C dates with precisions ∼100 (14)C years for materials deposited in the last 10,000 years and ∼300 (14)C years for carbon with (14)C ages of up to 20,000 years.

Measurement of multiply substituted isotopologues ('clumped isotopes') of CO2 using a 5 kV compact isotope ratio mass spectrometer: Performance, reference frame, and carbonate paleothermometry

RATIONALEnThe burgeoning field of clumped isotope paleothermometry, which has broad applications in geosciences, depends almost entirely on measurements made on two types of mass spectrometer with the same ion source design. Demonstration that these measurements can be carried out on a retrofitted mass spectrometer with a different type of ion source is important to the growing community of geoscientists considering employing this technique.nnnMETHODSnWe summarize the sample preparation techniques, mass spectrometry, and data processing involved in establishing an absolute reference frame for the measurement of Δ47 in CO2 from carbonate minerals using a prototype 5 kV mass spectrometer. The prototype differs from previously marketed mass spectrometers only in the presence of six extra Faraday cups designed specifically to measure ion beams of masses 44-49. We employ pressure baseline corrections on the small mass 47 signal.nnnRESULTSnThe system was fully capable of establishing absolute reference frames for clumped isotope carbonate paleothermometry, despite alternative use of the system for other types of measurements (carbonate δ(18)O and δ(13)C values, water δ(18)O and δ(2)H values via equilibration, and δ(13) C and δ(15)N values of sedimentary organic material) in different reference frames. Repeated measurements of CO2 from carbonate standards yielded external precisions comparable with those from other laboratories and adequate for paleothermometry to a precision of near or below ±5 °C. The accuracy was demonstrated by reasonable temperatures being obtained for different types of repeatedly measured carbonates. Measurements of the pressure baseline with every sample increased analysis times by 20 min, but decreased the stabilization time of the reference frame by days to weeks, while improving precision.nnnCONCLUSIONSnSimple modifications to existing instrumentation will allow more laboratories to perform clumped isotope measurements. The prototype mass spectrometer used herein provides precision comparable with all published data. We show that, where negatively charged species are associated with large ion beams, making pressure baseline corrections with every measurement is increasingly important no matter what instrument is used.

Carbonate clumped isotope analyses with the long‐integration dual‐inlet (LIDI) workflow: scratching at the lower sample weight boundaries

RATIONALEnClumped isotope analyses (Δ47 ) of carbonates by dual inlet (DI) mass spectrometry require long integration times to reach the necessary high precision due to the low abundance of the rare isotopologue 13 C18 O16 O. Traditional DI protocols reach this only with large amounts of sample and/or a large number of replicates as a large portion of the analyte gas is wasted. We tested an improved analytical workflow that significantly reduces the sample sizes and total analysis time per sample while preserving precision and accuracy.nnnMETHODSnWe implemented the LIDI (long-integration dual-inlet) protocol to measure carbonates in micro-volume mode using a Kiel IV carbonate device coupled to a Thermo Scientific 253 Plus isotope ratio mass spectrometer without the new 1013 ohm amplifier technology. The LIDI protocol includes a single measurement of the sample gas (600xa0s integration) followed by a single measurement of the working gas (WG) with the same integration time.nnnRESULTSnThe Δ47 measurements of four calcite standards over a period of 5xa0weeks demonstrate excellent long-term stability with a standard deviation of ±0.021 to ±0.025 ‰ for the final values of the individual aliquots. The Δ47 analyses of a coral, four foraminifera and a calcite precipitated in the laboratory demonstrate that 14 replicates of 90 to 120xa0μg are sufficient to achieve an external precision of ±0.007 ‰ (1SE) or of ±0.013 ‰ at the 95% confidence level.nnnCONCLUSIONSnThis study demonstrates that by using a Kiel IV-253 Plus system with LIDI it is possible to achieve the same analytical precision as conventional DI measurements with at least a factor of 40 less sample material. With the new 1013 ohm resistor technology there is the potential to reduce the required sample material even more. This opens new avenues of research in paleoceanography, paleoclimatology, low-temperature diagenesis and other currently sample size limited applications. Copyright

A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions

Carbonate clumped isotopes offer a potentially transformational tool to interpret Earths history, but the proxy is still limited by poor interlaboratory reproducibility. Here, we focus on the uncertainties that result from the analysis of only a few replicate measurements to understand the extent to which unconstrained errors affect calibration relationships and paleoclimate reconstructions. We find that highly precise data can be routinely obtained with multiple replicate analyses, but this is not always done in many laboratories. For instance, using published estimates of external reproducibilities we find that typical clumped isotope measurements (three replicate analyses) have margins of error at the 95% confidence level (CL) that are too large for many applications. These errors, however, can be systematically reduced with more replicate measurements. Second, using a Monte Carlo-type simulation we demonstrate that the degree of disagreement on published calibration slopes is about what we should expect considering the precision of Δ47 data, the number of samples and replicate analyses, and the temperature range covered in published calibrations. Finally, we show that the way errors are typically reported in clumped isotope data can be problematic and lead to the impression that data are more precise than warranted. We recommend that uncertainties in Δ47 data should no longer be reported as the standard error of a few replicate measurements. Instead, uncertainties should be reported as margins of error at a specified confidence level (e.g., 68% or 95% CL). These error bars are a more realistic indication of the reliability of a measurement.

Penultimate deglacial warming across the Mediterranean Sea revealed by clumped isotopes in foraminifera

The variability of seawater temperature through time is a critical measure of climate change, yet its reconstruction remains problematic in many regions. Mg/Ca and oxygen isotope (δ18OC) measurements in foraminiferal carbonate shells can be combined to reconstruct seawater temperature and δ18O (δ18OSW). The latter is a measure of changes in local hydrology (e.g., precipitation/evaporation, freshwater inputs) and global ice volume. But diagenetic processes may affect foraminiferal Mg/Ca. This restricts its potential in many places, including the Mediterranean Sea, a strategic region for deciphering global climate and sea-level changes. High alkalinity/salinity conditions especially bias Mg/Ca temperatures in the eastern Mediterranean (eMed). Here we advance the understanding of both western Mediterranean (wMed) and eMed hydrographic variability through the penultimate glacial termination (TII) and last interglacial, by applying the clumped isotope (Δ47) paleothermometer to planktic foraminifera with a novel data-processing approach. Results suggest that North Atlantic cooling during Heinrich stadial 11 (HS11) affected surface-water temperatures much more in the wMed (during winter/spring) than in the eMed (during summer). The method’s paired Δ47 and δ18OC data also portray δ18OSW. These records reveal a clear HS11 freshwater signal, which attenuated toward the eMed, and also that last interglacial surface warming in the eMed was strongly amplified by water-column stratification during the deposition of the organic-rich (sapropel) interval known as S5.

Short organic carbon turnover time and narrow 14C age spectra in early Holocene wetland paleosols

U.S. Department of Energy through the National Institute for Climatic Change Research Coastal Center; National Science Foundation [OCE-1502588, OCE-1502753]; Tulane University

Ventilation time scales of the North Atlantic subtropical cell revealed by coral radiocarbon from the Cape Verde Islands

We present coral- and sclerosponge-based reconstructions of the 14C content in North Atlantic dissolved inorganic carbon (DIC) during the last ~100u2009years from the subtropical cells (STCs). These waters are sensitive to the dynamics of the shallow overturning meridional circulation that transports heat and water masses from the subtropics to the tropics. We use these records to investigate the circulation patterns of the off-equatorial upwelling regions of the STCs, which are not well understood. Coral and sclerosponge skeletons provide long time series of ocean DIC 14C content, a tracer of oceanic circulation, effectively extending the observational record back in time. Sclerosponge data from the Bahamas were used to extend the existing subtropical 14C time series to the 21st century. Coral 14C data from the Cape Verde Islands (1890–2002) captured the 14C signature of water brought to the surface in the off-equatorial regions of the STC present near the West African coast. We observe a unique postbomb trend at Cape Verde that is similar to the upwelling regions in the Pacific, and we interpret this trend as the result of the slow penetration of bomb 14C into the interior ocean as part of the STC circulation. Using a multibox mixing model we constrain the time history of bomb 14C in the eastern tropical Atlantic, and we estimate a 20u2009year time scale for ventilation of the thermocline in this area of the ocean. The similarity between the Atlantic and Pacific 14C-based records of upwelling suggests that both are caused by bomb 14C penetration rather than more complex explanations that invoke changes in thermocline depth (e.g., related to El Nino–Southern Oscillation variability) or changes in the strength of the subtropical cells. Our results offer constraints for models of tropical ocean circulation and anthropogenic CO2 uptake that attempt to reproduce the characteristics of the shallow wind-driven circulation in the Atlantic.