Binding characteristics of metal ions (Li + , Cd 2+ , Zn 2+ , Cu 2+ ) with humic substances (HSs) are investigated by first principle calculation at BP86/SDD level. In the present work, HSs are well represented by singly deprotonated alkyl/aryl carboxylic acid. The results reveal that the bidentate is the strongest complexation form. Moreover, with the increase of ionic potential, the binding energies of HSs to chelate metal ions increase in order, Li + < Cd 2+ < Zn 2+ < Cu 2+ . The nature of the ligand also exerts important influence on the stability of organometallic complexes. Specifically, for Li + , the ionic bond-forming part occurs as electroneutrality. Whatever electrondonating groups or electron-withdrawing groups including alkyl, aryl and its derivatives (salicylic acid and m (p)-substituted gallic acid by hydroxyl or amino) and carbon-carbon double bond connects to the carboxylate group, the electron density of the ionic bond-forming part will be changed resulting in the decrease of binding energy (BE). However, for ions with high ionic potential or high positive charge density (Cd 2+ , Cu 2+ and Zn 2+ ), the ionic bond-forming part is positively charged. From electron-withdrawing groups to electron-donating groups, the extent to deviate from electroneutrality is gradually decreased, although the quantity of electron is possibly insufficient to balance the extra positive charge. As a result, the BE value gradually increases, but does not reach a maximum for studied ions and ligands. Besides, mixed functional groups are able to stabilize organometallic complexes. The optimal mixed functional group is carboxyl and hydroxyl on ortho position, followed by two hydroxyls, hydroxyl and carbonyl, carboxyl and carbonyl, In the end, the geochemical behavior of trace elements in coalification is predicted: small organic acids generated by decomposition of dead plants in relatively oxidized environments will facilitate the enrichment of lithium and this proportion of lithium will be released into pore water in the polymerization of small molecules, possibly accumulating in secondary minerals in low-rank coals; metal ions with high ionic potential bonded by organic molecules will be released in a later stage and accumulate in slightly higher rank coals.

Trace element enrichment in coals has increasingly been focused in the community of coal geochemistry. To research the enrichment mechanism of trace element in coals on molecular/atomic scale is an important complement of field investigations, but relevant works are scattered. In the present work, the effect of local structure on the ability of main oxygen-containing groups to chelate trace element metal ions including -COO À and C 6 H 5 O À is preliminarily quantified. It is completed by evaluating the Mulliken charge excess n, i.e. the sum of Mulliken charge for metal ions and atoms involved in chelating functional groups. When electron-donating groups like benzene and its derivatives immediately connect to cation carboxylates, excess electron will be transferred to cation carboxylates, pulling down the n values and stabilizing metal-humate complexes. Otherwise, electron-withdrawing groups like C ¼ C, CC, and C ¼ O play a contrary role. Based on calculations, at the vicinity of n % 0, the binding energy is highest. For monovalent cation ions, the most stable metal-humate complex is that chelated by small alkyl carboxylate, while the highest binding energy is not found for high-valent cation ions in the investigation. Meanwhile, both the combination of hydroxyl and carboxyl and hydroxyls have

The extensive gneisses in the high‐pressure and ultrahigh‐pressure metamorphic terrane in the Dabie‐Sulu orogen usually show no evidence of eclogite‐facies metamorphism. The garnet‐mica‐plagioclase gneisses from the Qiliping region in the western Dabie Orogen, comprise garnet, phengite, biotite, plagioclase, quartz, rutile, ilmenite, chlorite, epidote, and hornblende. The garnet porphyroblasts, with inclusions of quartz, epidote, and rutile, exhibit slight compositional zonations, from core to mantle with an increase in pyrope and a decrease in spessartine, and from mantle to rim with a decrease in pyrope and grossular and an increase in spessartine. The high‐Si phengite indicates that the gneisses may be subjected to a high‐pressure metamorphism. By the P–T pseudosections calculated in a system NCKMnFMASHTO (Na2O‐CaO‐K2O‐MnO‐FeO‐MgO‐Al2O3‐SiO2‐H2O‐TiO2‐O) for two representative samples, the metamorphic P–T path, reconstructed by the compositionally zoned garnet, shows that the prograde metamorphism is characterized by a temperature increase with a slight pressure increase from the conditions of 17.6 ± 1.5 kbar at 496 ± 15°C to the peak‐pressure ones of 21.8 ± 1.5–22.7 ± 1.5 kbar at 555 ± 15–561 ± 15°C; the early retrograde stage is dominated by decompression with a temperature increase to the maximum of 608 ± 15–611 ± 18°C at 10.3 ± 1.5–11.0 ± 1.5 kbar; and the late retrograde one is predominated by pressure and temperature decreases. The mineral assemblages in the prograde metamorphism are predicted to contain garnet, glaucophane, jadeite, lawsonite, phengite, quartz, rutile, and/or chlorite, which is different from those observed at present. Such high‐pressure metamorphism can partly be reconstructed by the P–T pseudosection in combination with the high‐Si phengite and garnet compositions in the core and mantle. This provides an important constraint on the subduction and exhumation of the terrane during the continent–continent collision between the Yangtze and Sino‐Korean cratons.