TIMS measurements of full range of natural Ca isotopes with internally consistent fractionation correction

This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus™ thermal ionization mass spectrometer with a specially developed Faraday cup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept < 1 µg. With this setup the measurement uncertainties were 0.06 ‰ for 40Ca/44Ca and 0.12 ‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature. The exponential law was observed to correct incompletely instrumental mass fractionation. An improved fractionation correction based on the exponential law is proposed. It changes the 40Ca/44Ca ratio of SRM 915a (corrected relative to 42Ca/44Ca = 0.31221; 48Ca/44Ca = 0.08871) from 47.1635 ± 0.0028 to 47.1649 ± 0.0047. The measurements of SRM 915b were performed with different analytical conditions (runs were prolonged till complete filament load depletion). Even if the 40Ca/44Ca ratio of SRM 915b, when corrected with the simple exponential law, appears different (47.1532 ± 0.0038) from that of SRM 915a, it becomes coincident (47.1613 ± 0.0028) when corrected with a second-order refinement. This supports the use of the improved exponential law to obtain internally consistent Ca isotope ratio for natural samples.

Late Quaternary palaeoenvironmental reconstruction from Lakes Ohrid and Prespa (Macedonia/Albania border) using stable isotopes

Abstract. Here we present stable isotope data from three sediment records from lakes that lie along the Macedonian- Albanian border (Lake Prespa: 1 core, and Lake Ohrid: 2 cores). The records only overlap for the last 40 kyr, although the longest record contains the MIS 5/6 transition (Lake Ohrid). The sedimentary characteristics of both lakes differ significantly between the glacial and interglacial phases. At the end of MIS 6 Lake Ohrid’s water level was low (high �18Ocalcite) and, although productivity was increasing (high calcite content), the carbon supply was mainly from inorganic catchment rock sources (high �13Ccarb). During the last interglacial, calcite and TOC production and preservation increased, progressively lower �18Ocalcite suggest increase in humidity and lake levels until around 115 ka. During ca. 80 ka to 11 ka the lake records suggest cold conditions as indicated by negligible calcite precipitation and low organic matter content. In Lake Ohrid, �13Corg are complacent; in contrast, Lake Prespa shows consistently higher �13Corg suggesting a low oxidation of 13C-depleted organic matter in agreement with a general deterioration of climate conditions during the glacial. From 15 ka to the onset of the Holocene, calcite and TOC begin to increase, suggesting lake levels were probably low (high �18Ocalcite). In the Holocene (11 ka to present) enhanced productivity is manifested by high calcite and organic matter content. All three cores show an early Holocene characterised by low �18Ocalcite, apart from the very early Holocene phase in Prespa where the lowest �18Ocalcite occurs at ca. 7.5 ka, suggesting a phase of higher lake level only in (the more sensitive) Lake Prespa. From 6 ka, �18Ocalcite suggest progressive aridification, in agreement with many other records in the Mediterranean, although the uppermost sediments in one core records low �18Ocalcite which we interpret as a result of human activity. Overall, the isotope data present here confirm that these two big lakes have captured the large scale, low frequency palaeoclimate variation that is seen in Mediterranean lakes, although in detail there is much palaeoclimate information that could be gained, especially small scale, high frequency differences between this region and the Mediterranean.

Evidence for extinct Cs-135 from Ba isotopes in Allende CAIs?

he abundance and distribution of isotopes throughout the Solar System can be used to constrain the number and type of nucleosynthetic events that contributed material to the early nebula. Barium is particularly well suited to quantifying the degree of isotope heterogeneity in the Solar System because it comprises seven stable isotopes that were synthesized by three different nucleosynthetic processes (s-, r-, and p-processes), all of which contributed material to the Solar System. There is also potential contribution to 135Ba from short-lived radioisotope 135Cs, conclusive evidence for which is yet to be reported. Four Allende (CV3) Ca,Al-rich inclusions (CAI 1, CAI 2, CAI 4, CAI 5) and one Allende dark inclusion (DI) were analyzed for Ba isotope variability. Two CAIs (CAI 2 and CAI 5) display 135Ba excesses that are not accompanied by 137Ba anomalies. Calcium–aluminum-rich inclusion 1 displays a 135Ba excess that is possibly coupled with a 137Ba excess, and the remaining refractory inclusions (CAI 2 and DI) have terrestrial Ba isotope compositions. These Ba isotope data are presented in conjunction with published whole rock Ba isotope data from individual Allende CAIs. The enrichment in 135Ba and absence of coupled 137Ba excesses in CAI 2 and CAI 5 is interpreted to indicate that the anomalies are not purely nucleosynthetic in origin but also contain contributions (16–48 ppm) from the decay of short-lived 135Cs. The majority of Allende CAIs studied to date may also have similar contributions from 135Cs on the basis of higher than expected 135Ba excesses if the Ba isotope anomalies were purely nucleosynthetic in origin. The 135Ba anomalies appear not to be coupled with superchondritic Cs/Ba, which may imply that the contribution to 135Ba did not occur via in situ decay of live 135Cs. However, it is feasible that the CAIs had a superchondritic Cs/Ba during decay of 135Cs, but Cs was subsequently removed from the system during aqueous alteration on the parent body. An alternative scenario is the potential existence of a transient high-temperature reservoir having superchondritic Cs/Ba in the early Solar System while 135Cs was extant, which enabled a radiogenic 135Ba signature to develop in some early condensates. The nucleosynthetic source of 135Cs can be determined by reconciling the predicted astrophysical 135Cs abundance with its measured abundance in meteorites. Further, the currently accepted initial 135Cs/133Cs of the Solar System, [135Cs/133Cs]0, may be underestimated because the spread of Cs/Ba among samples is small and the range of excess 135Ba is limited thus leading to inaccuracies when estimating [135Cs/133Cs]0. If the initial meteoritic abundance of 135Cs was indeed higher than is currently thought, the most probable stellar source of short-lived radioisotopes was a nearby core-collapse supernova and/or the Wolf–Rayet wind driven by its progenitor.

Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO2 rise

The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global three-dimensional ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during the early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.