About a decade after its introduction, the field of carbonate clumped isotope thermometry is rapidly expanding because of the large number of possible applications and its potential to solve long‐standing questions in Earth Sciences. Major factors limiting the application of this method are the very high analytical precision required for meaningful interpretations, the relatively complex sample preparation procedures, and the mass spectrometric corrections needed. In this paper we first briefly review the evolution of the analytical and standardization procedures and discuss the major remaining sources of uncertainty. We propose that the use of carbonate standards to project the results to the carbon dioxide equilibrium scale can improve interlaboratory data comparability and help to solve long‐standing discrepancies between laboratories and temperature calibrations. The use of carbonates reduces uncertainties related to gas preparation and cleaning procedures and ensures equal treatment of samples and standards. We present a set of carbonate standards of diverse composition, discuss how they can be used to correct for mass spectrometric biases, and demonstrate that their use significantly improves the comparability among four laboratories. We propose that the use of these standards or of a similar set of carbonate standards will improve the comparability of data across laboratories.
The exclusive use of carbonate reference materials is a robust method for the standardization of clumped isotope measurements • Measurements using different acid temperatures, designs of preparation lines, and mass spectrometers are statistically indistinguishable • We propose new consensus values for a set of 7 carbonate reference materials and updated guidelines to report clumped isotope measurements
Encoded self-assembling chemical (ESAC) libraries are characterized by the covalent display of chemical moieties at the extremity of self-assembling oligonucleotides carrying a unique DNA sequence for the identification of the corresponding chemical moiety. We have used ESAC library technology in a two-step selection procedure for the identification of novel inhibitors of stromelysin-1 (MMP-3), a matrix metalloproteinase involved in both physiological and pathological tissue remodeling processes, yielding novel inhibitors with micromolar potency.
Using biodegradable instead of conventional plastics in agricultural applications promises to help overcome plastic pollution of agricultural soils. However, analytical limitations impede our understanding of plastic biodegradation in soils. Utilizing stable carbon isotope (13C-)labelled poly(butylene succinate) (PBS), a synthetic polyester, we herein present an analytical approach to continuously quantify PBS mineralization to 13CO2 during soil incubations and, thereafter, to determine non-mineralized PBS-derived 13C remaining in the soil. We demonstrate extensive PBS mineralization (65 % of added 13C) and a closed mass balance on PBS−13C over 425 days of incubation. Extraction of residual PBS from soils combined with kinetic modeling of the biodegradation data and results from monomer (i.e., butanediol and succinate) mineralization experiments suggest that PBS hydrolytic breakdown controlled the overall PBS biodegradation rate. Beyond PBS biodegradation in soil, the presented methodology is broadly applicable to investigate biodegradation of other biodegradable polymers in various receiving environments.
Breath and diet samples were collected from 29 taxa of animals at the Zurich and Basel Zoos to characterize the carbon isotope enrichment between breath and diet. Diet samples were measured for δ13C and breath samples for CH4/CO2 ratios and for the respired component of δ13C using the Keeling plot approach. Different digestive physiologies included coprophagous and non-coprophagous hindgut fermenters, and non-ruminant and ruminant foregut fermenters. Isotope enrichments from diet to breath were 0.8 ± 0.9‰, 3.5 ± 0.8‰, 2.3 ± 0.4‰, and 4.1 ± 1.0‰, respectively. CH4/CO2 ratios were strongly correlated with isotope enrichments for both hindgut and foregut digestive strategies, although CH4 production was not the sole reason for isotope enrichment. Average CH4/CO2 ratios per taxon ranged over several orders of magnitude from 10–5 to 10–1. The isotope enrichment values for diet-breath can be used to further estimate the isotope enrichment from diet-enamel because Passey et al. (2005b) found a nearly constant isotope enrichment for breath-enamel for diverse mammalian taxa. The understanding of isotope enrichment factors from diet to breath and diet to enamel will have important applications in the field of animal physiology, and possibly also for wildlife ecology and paleontology.
Abstract. A better understanding of ENSO dynamics is essential for modelling future climate change and its impacts on the ecosystems and lives of the inhabitants of the tropical Pacific islands, which face considerable environmental risk in the coming decades. This study reconstructs past ENSO dynamics using a multi-proxy approach applied to a stalagmite from Niue Island that covers the period 6.4–5.4 ka BP. δ18O and δ13C, trace-element concentrations and image analysis are linked to an age-depth model constrained by eight U/Th dates and a complete lamina count. Principal component analysis of the proxy time series reveals hydrological changes at seasonal scale that are expressed in differential stalagmite lamina growth and geochemical characteristics. Increased concentrations of host-rock derived elements (Mg/Ca and U/Ca) and higher δ18O and δ13C values are observed in the dark, dense calcite laminae that are deposited during the dry season, whereas during the wet season higher concentrations of soil derived elements (Zn/Ca, Mn/Ca) and higher δ18O and δ13C values are found in pale, porous calcite laminae. Greyscale intensity values measured along the stalagmite growth axis are used here as an indicator of colour and density changes of the alternating laminae, allowing for the construction of a further seasonality record which expresses the contrast between wet and dry seasons. The multi-proxy record from Niue shows seasonal cycles associated with hydrological changes controlled by the South Pacific convergence zone. Wavelet analysis of the greyscale record reveals that ENSO was continuously active during the depositional period, with two weaker intervals at 6–5.9 and 5.6–5.5 ka BP. ENSO activity is also observed in the seasonality record, but muted periods are more prolonged, and intervals of significant ENSO-band power are more episodic. Recurrence analysis of nonlinear behaviour shows the influence that ENSO activity exerts on seasonality patterns and allows us to quantify the predictability of the climate system. Our results suggest that recurrence in the seasonal cycle of rainfall was reduced during periods when ENSO activity was stronger, pushing the system towards stochastic conditions. The tipping points from stochastic to predictable conditions may represent transitions in the Tropical Pacific mean state.
Ocean acidification increases pCO2 and decreases pH of seawater and its impact on marine organisms has emerged as a key research focus. In addition to directly measured variables such as growth or calcification rate, stable isotopic tracers such as carbon isotopes have also been used to more completely understand the physiological processes contributing to the response of organisms to ocean acidification. To simulate ocean acidification in laboratory cultures, direct bubbling of seawater with CO2 has been a preferred method because it adjusts pCO2 and pH without altering total alkalinity. Unfortunately, the carbon isotope equilibrium between seawater and CO2 gas has been largely ignored so far. Frequently, the dissolved inorganic carbon (DIC) in the initial seawater culture has a distinct 13C/12C ratio which is far from the equilibrium expected with the isotopic composition of the bubbled CO2. To evaluate the consequences of this type of experiment for isotopic work, we measured the carbon isotope evolutions in two chemostats during CO2 bubbling and composed a numerical model to simulate this process. The isotopic model can predict well the carbon isotope ratio of dissolved inorganic carbon evolutions during bubbling. With help of this model, the carbon isotope evolution during a batch and continuous culture can be traced dynamically improving the accuracy of fractionation results from laboratory culture. Our simulations show that if not properly accounted for in experimental or sampling design, many typical culture configurations involving CO2 bubbling can lead to large errors in estimated carbon isotope fractionation between seawater and biomass or biominerals, consequently affecting interpretations and hampering comparisons among different experiments. Therefore, we describe the best practices on future studies working with isotope fingerprinting in the ocean acidification background.
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