Comprehensive metabolome characterization and comparison between two sources of Dragon's blood by integrating liquid chromatography/mass spectrometry and chemometrics.

Dragon's Blood (DB) serves as a precious Chinese medicine facilitating blood circulation and stasis dispersion. Daemonorops draco (D. draco; Qi-Lin-Jie) and Dracaena cochinchinensis (D. cochinchinenesis; Long-Xue-Jie) are two reputable plant sources for preparing DB. This work was designed to comprehensively characterize and compare the metabolome differences between D. draco and D. cochinchinenesis, by integrating liquid chromatography/mass spectrometry and untargeted metabolomics analysis. Offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (2D-LC/IM-QTOF-MS), by utilizing a powerful hybrid scan approach, was elaborated for multicomponent characterization. Configuration of an XBridge Amide column and an HSS T3 column in offline mode exhibited high orthogonality (A0 0.80) in separating the complex components in DB. Particularly, the hybrid high-definition MSE-high definition data-dependent acquisition (HDMSE-HDDDA) in both positive and negative ion modes was applied for data acquisition. Streamlined intelligent data processing facilitated by the UNIFI™ (Waters) bioinformatics platform and searching against an in-house chemical library (recording 223 known compounds) enabled efficient structural elucidation. We could characterize 285 components, including 143 from D. draco and 174 from D. cochinchinensis. Holistic comparison of the metabolomes among 21 batches of DB samples by the untargeted metabolomics workflows unveiled 43 significantly differential components. Separately, four and three components were considered as the marker compounds for identifying D. draco and D. cochinchinenesis, respectively. Conclusively, the chemical composition and metabolomic differences of two DB resources were investigated by a dimension-enhanced analytical approach, with the results being beneficial to quality control and the differentiated clinical application of DB.

Natural stable calcium isotope ratios: a new gold standard for bone balance?

Bone calcium balance is the net gain, loss, or equilibrium of calcium moving to and from bone, which reflects bone balance. There are currently no clinically available tools for measuring real-time bone balance. In this issue, Shroff et al. demonstrate the use of natural stable calcium isotope ratios as a novel biomarker of bone balance in children with chronic kidney disease on dialysis that is highly repeatable and associated with radiological and biochemical markers of bone metabolism.

Determination of Picogram-per-Gram Concentrations of 231Pa and 230Th in Sediments by Melt Quenching and Laser Ablation Mass Spectrometry.

Uranium, thorium, and protactinium radionuclides in marine sediments are important proxies for understanding the earth's environmental evolution. Conventional solution-based methods, which typically involve isotope spike preparation, concentrated acid sample digestion, column chemistry, and mass spectrometry, allow precise but time-consuming and costly measurements of these nuclide concentrations (i.e., 230Th and 231Pa). In this work, we have established an efficient method for 230Th and 231Pa measurement of marine sediments down to the picogram-per-gram level without purification and enrichment. Our method first transforms a small amount of thermally decomposed sediments (∼0.1-0.2 g) to homogeneous silicate glass using a melt quenching technique and then analyzes the glass with laser ablation multicollector inductively coupled plasma-mass spectrometry. Standard sample bracketing with isotope-spike-calibrated glass standards prepared in this study was used to correct for instrumental fractionation during measurement. It is demonstrated that our method can accurately determine the U-Th-Pa concentrations of typical marine sediments in the late Pleistocene with precision of a few percent. Compared with the conventional solution-based methods, the turnover time of sample preparation and measurement with our established protocol is greatly reduced, facilitating future application of U-series radionuclides in reconstructing oceanic processes at high temporal and spatial resolution.

Geochemistry and Cosmochemistry of Potassium Stable Isotopes.

Stable potassium isotopes are one of the emerging non-traditional isotope systems enabled in recent years by the advance of Multi-Collector Inductively-Coupled-Plasma Mass-Spectrometry (MC-ICP-MS). In this review, we first summarize the geochemical and cosmochemical properties of K, its major reservoirs, and the analytical methods of K isotopes. Following this, we review recent literature on K isotope applications in the fields of geochemistry and cosmochemistry. Geochemically, K is a highly incompatible lithophile element, and a highly soluble, biophile element. The isotopic fractionation of K is relatively small during magmatic processes such as partial melting and fractional crystallization, whereas during low-temperature and biological processes fractionation is considerably larger. This resolvable fractionation has made K isotopes promising tracers for a variety of Earth and environmental processes, including chemical weathering, low-temperature alteration of igneous rocks, reverse weathering, and the recycling of sediments into the mantle during subduction. Sorption and interactions of aqueous K with different clay minerals during cation exchange and clay formation are likely to be of fundamental significance in generating much of the K isotope variability seen in samples from the Earth surface and samples carrying recycled surface materials from the deep Earth. The magnitude of this fractionation is process- and mineral-dependent. Comprehensive quantification of pertinent K isotope fractionation factors is currently lacking and urgently needed. Significant fractionation during biological activities, such as plant uptake, demonstrates the potential utility of K isotopes in the study of the nutrient cycle and its relation to the climate and various ecosystems, enabling new and largely unexplored avenues for future research. Of significant importance to the cosmochemistry community, K is a moderately volatile element with large variations in K/U ratio observed among chondrites and planetary materials. As this indicates different degrees of volatile depletion, it has become a fundamental chemical signature of both chondritic and planetary bodies. This volatile depletion has been attributed to various processes such as solar nebula condensation, mixing of volatile-rich and -poor reservoirs, planetary accretional volatilization via impacts, and/or magma ocean degassing. While K isotopes have the potential to distinguish these different processes, the current results are still highly debated. A good correlation between the K isotope compositions of four differentiated bodies (Earth, Mars, Moon, and Vesta) and their masses suggests a ubiquitous volatile depletion mechanism during the formation of the terrestrial planets. It is still unknown whether any of the K isotopic variation among chondrites and differentiated bodies can be attributed to inherited signatures of mass-independent isotopic anomalies.