Quantitative reconstruction of a single super rainstorm using daily resolved δ18O of land snail shells.

A "once-in-a-millennium" super rainstorm battered Zhengzhou, central China, from 07/17/2021 to 07/22/2021 (named "7.20" Zhengzhou rainstorm). It killed 398 people and caused billions of dollars in damage. A pressing question is whether rainstorms of this intensity can be effectively documented by geological archives to understand better their historical variabilities beyond the range of meteorological data. Here, four land snail shells were collected from Zhengzhou, and weekly to daily resolved snail shell δ18O records from June to September of 2021 were obtained by gas-source mass spectrometry and secondary ion mass spectrometry. The daily resolved records show a dramatic negative shift between 06/18/2021 and 09/18/2021, which has been attributed to the "7.20" Zhengzhou rainstorm. Moreover, the measured amplitude of this shift is consistent with the theoretical value estimated from the flux balance model and instrumental data for the "7.20" Zhengzhou rainstorm. Our results suggest that the ultra-high resolution δ18O of land snail shells have the potential to reconstruct local synoptic scale rainstorms quantitatively, and thus fossil snail shells in sedimentary strata can be valuable material for investigating the historical variability of local rainstorms under different climate backgrounds.

Three-Dimensional Elemental Imaging of Nantan Meteorite via Femtosecond Laser Ionization Time-of-Flight Mass Spectrometry.

Femtosecond laser ionization time-of-flight mass spectrometry (fs-LI-TOFMS) is introduced for the three-dimensional elemental analysis of a Nantan meteorite. Spatially resolved multielemental imaging of major and minor compositions in a meteorite are presented with a lateral resolution of 50 µm and a depth resolution of 7 µm. Distinct 3D distributions of siderophile, lithophile, and chalcophile elements are revealed. Co and Ni are highly siderophile (Iron-loving), mainly enriched in the metal phase. Cr, Cu, V, and Mn are enriched in the sulfide for their chalcophile (S-loving) tendency. S, P, and C aggregate together in the analytical volume. Silicate inclusion, containing lithophile elements of Al, Ca, Mg, K, and so on, is embedded within the metal phase for the immiscibility between silicate inclusion and the melted metal phase. These 3D distributions of elements aid the exploration of the formation and evolution of the meteorite. They also reveal the feasibility of fs-LI-TOFMS as a versatile tool for 3D imaging.

[Mass Spectrometric Methods for Colorative Mechanism Analysis of Yaozhou Porcelain Glaze].

An in-house-built femtosecond laser ionization time-of-flight mass spectrometry (fs-LI-TOFMS) has been applied to the multi-elemental analysis of porcelain glaze from Yaozhou kiln. The samples are selected representing products of different dynasties, including Tang, Five, Song, Jin, and Ming Dynasty. For exploring the colorative mechanism of Yaozhou porcelain through the elemental analysis of the glaze, the effects of all potential coloring elements, especially transition elements, were considered. There was a speculation that the typical Co-Cr-Fe-Mn recipe was used in the fabrication of Yaozhou black glaze; the low content of Fe and high content of Ni resulted in the porcelain of white glaze; an increase content of P could lead the porcelain to be yellow-glazed. Undoubtedly, this research is an important supplement to the study of the colorative mechanism of the Yaozhou porcelain system.

Thermal diffusion desorption for the comprehensive analysis of organic compounds.

Comprehensive analysis of organic compounds is crucial yet challenging considering that information on elements, fragments, and molecules is unavailable simultaneously by current analytical techniques. Additionally, many compounds are insoluble or only dissolve in toxic solvents. A solvent- and matrix-free strategy has been developed which allows the organic compound analyzed in its original form. It utilizes thermal diffusion desorption with the solid analyte irradiated with high energy laser. It is capable of providing explicit elemental, fragmental, and molecular information simultaneously for a variety of organic compounds. Thermal diffusion desorption has many advantages compared to the electrospray and MALDI techniques. The protons that form the protonated molecular ions originate from the analyte itself. All the elements and fragments are also derived from the analyte itself, which provides abundant information and expedites the identification of organic compounds.

Single-cell elemental analysis via high irradiance femtosecond laser ionization time-of-flight mass spectrometry.

In modern bioanalytics, elemental analysis of single cells is important yet challenging due to the complicated biological matrices and elemental contents. We have developed the high irradiance femtosecond laser ionization orthogonal time-of-flight mass spectrometry (fs-LI-O-TOFMS) to determine the elemental composition of individual cells. The sample preparation procedure is simple and fast through heating and drying the cells. Under typical operating conditions, elements above femtogram levels in a single cell can be clearly observed in the spectrum with reasonable isotope ratios. Some of the nonmetallic elements that are difficult to measure by ICPMS, such as P, S, and Cl, can be easily determined by fs-LI-O-TOFMS. Replicate analyses show that signal variations are 15-35% for metallic elements and 25-50% for nonmetallic elements. The results demonstrate that fs-LI-O-TOFMS is a simple, rapid, and practical tool for the elemental determination of single cells.

Minimizing matrix effect by femtosecond laser ablation and ionization in elemental determination.

Matrix effect is unavoidable in direct solid analysis, which usually is a leading cause of the nonstoichiometric effect in quantitative analysis. In this research, experiments were carried out to study the overall characteristics of atomization and ionization in laser-solid interaction. Both nanosecond (ns) and femtosecond (fs) lasers were applied in a buffer-gas-assisted ionization source coupled with an orthogonal time-of-flight mass spectrometer. Twenty-nine solid standards of ten different matrices, including six metals and four dielectrics, were analyzed. The results indicate that the fs-laser mode offers more stable relative sensitivity coefficients (RSCs) with irradiance higher than 7 × 10(13) W·cm(-2), which could be more reliable in the determination of element composition of solids. The matrix effect is reduced by half when the fs-laser is employed, owing to the fact that the fs-laser ablation and ionization (fs-LAI) incurs an almost heat-free ablation process and creates a dense plasma for the stable ionization.