The nuclear volume effects (NVEs) of Hg, Tl and Pb isotope systems are investigated with careful evaluation on quantum relativistic effects via the Dirac’s formalism of full-electron wave function. Equilibrium ²⁰²Hg/¹⁹⁸Hg, ²⁰⁵Tl/²⁰³Tl, ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb isotope fractionations are found can be up to 3.61‰, 2.54‰, 1.48‰ and 3.72‰ at room temperature, respectively, larger than fractionations predicted by classical mass-dependent isotope fractionations theory. Moreover, the NVE can cause mass-independent fractionations (MIF) for odd-mass isotopes and even-mass isotopes. The plot of "Equation missing"<!-- image only, no MathML or LaTex -->vs. "Equation missing"<!-- image only, no MathML or LaTex --> for Hg-bearing species falls into a straight line with the slope of 1.66, which is close to previous experimental results. For the first time, Pb⁴⁺-bearing species are found can enrich heavier Pb isotopes than Pb²⁺-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of ²⁰⁸Pb/²⁰⁶Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb²⁺-bearing species are trivial. Therefore, the large Pb fractionation changes provide a potential new tracer for redox conditions in young and closed geologic systems. The magnitudes of NVE-driven even-mass MIFs of Pb isotopes (i.e., "Equation missing"<!-- image only, no MathML or LaTex -->) and odd-mass MIFs (i.e., "Equation missing"<!-- image only, no MathML or LaTex -->) are almost the same but with opposite signs.

Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H₄SiO₄ solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth’s surface environments. The results reveal that, in comparison to aqueous H₄SiO₄, heavy Si isotopes will be significantly enriched in secondary silicate minerals. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of ²⁸Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated, and the results support the previous statement that highly ²⁸Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With the equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many of Earth’s surface systems can be explained. For example, the change of bulk soil δ³⁰Si can be predicted as a concave pattern with respect to the weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches their maximum. When, under equilibrium conditions, the well-crystallized clays start to precipitate from the pore solutions, the bulk soil δ³⁰Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ³⁰Si variations in the ground water profile. The equilibrium Si isotope fractionations among the quadra-coordinated organosilicon complexes and the H₄SiO₄ solution may also shed light on the Si isotope distributions in the Si-accumulating plants.

An anomalous isotope effect exists in many heavy element isotope systems (e.g., Sr, Gd, Zn, U). This effect used to be called the “odd–even isotope effect” because the odd mass number isotopes behave differently from the even mass number isotopes. This mass-independent isotope fractionation driving force, which originates from the difference in the ground-state electronic energies caused by differences in nuclear size and shape, is currently denoted as the nuclear field shift effect (NFSE). It is found that the NFSE can drive isotope fractionation of some heavy elements (e.g., Hg, Tl, U) to an astonishing degree, far more than the magnitude caused by the conventional mass-dependent effect (MDE). For light elements, the MDE is the dominant factor in isotope fractionation, while the NFSE is neglectable. Furthermore, the MDE and the NFSE both decrease as temperatures increase, though at different rates. The MDE decreases rapidly with a factor of 1/T², while the NFSE decreases slowly with a factor of 1/T. As a result, even at high temperatures, the NFSE is still significant for many heavy element isotope systems. In this review paper, we begin with an introduction of the basic concept of the NSFE, including its history and recent progress, and follow with the potential implications of the inclusion of the NFSE into the kinetic isotope fractionation effect (KIE) and heavy isotope geochronology.

Vegetation restoration has become a common practice in karst rocky desertification (KRD) areas of southwestern China. The bacteria, which have made a connection between soil and plants, have been an important role in regulating the succession and restoration of karst vegetation. However, it is still unclear how soil bacterial communities and soil properties respond to natural vegetation restoration processes in karst areas. To address this gap, we investigated the soil nutrients, enzyme activity, and soil bacterial community among various plant communities, including farmland (FL), land with herbs only (SSI), herb-and-shrub land (SSII), woody thickets (SSIII), coniferous forest (SSIV), coniferous and broad-leaved mixed forest (SSV), and evergreen broad-leaved forest (SSVI). Our results found that SSII had the highest levels of soil organic matter, total nitrogen, available phosphorus, available nitrogen, sucrase, and β-glucosidase among all the plant communities. These results indicated that herb-and-shrub land have contributed to the rapid restoration of vegetation in KRD regions. FL exhibited the lowest levels of soil nutrients and enzyme activities, while showing the highest bacterial richness and diversity among all the plant communities. This suggested that appropriate human intervention can increase bacterial diversity and richness in the area. The predominant bacterial phylum also varied among the different plant communities, withActinobacteriabeing the most abundant in SSI, SSII, SSIII, and SSIV, whileProteobacteriawere the most abundant in SSV and SSVI. Furthermore, PCoA analysis demonstrated significant changes in the soil bacterial community structure, with SSI, SSII, SSIII, and SSIV had shared similar structures, while SSV and SSVI had comparable structures. As for soil characteristics, total phosphorus (TP) and total potassium (TK) were the primary factors affecting the soil bacterial community. SSV and SSVI had the most complex bacterial networks and were more stable than other groups. The generaKtedonobacter,norank_f_Anaerolineaceae, andVicinamibacterhad the highest betweenness centrality scores and were identified as keystone genera in the co-occurrence network in KRD areas. In summary, our results have demonstrated that herb-and-shrub can promote community succession and increase soil nutrient levels in KRD regions.