Enhanced Cr(VI) stabilization by terrestrial-derived soil protein: Photoelectrochemical properties and reduction mechanisms.

Glomalin-related soil protein (GRSP) is a stable iron-organic carbon mixture that can enhance heavy metal sequestration in soils. However, the roles of GRSP in the transformation and fate of Cr(VI) have been rarely reported. Herein, we investigated the electrochemical and photocatalytic properties of GRSP and its mechanisms in Cr(VI) adsorption and reduction. Results showed that GRSP had a stronger ability for Cr(VI) adsorption and reduction than other biomaterials, with the highest adsorption amount of up to 0.126 mmol/g. The removal efficiency of Cr(VI) by GRSP was enhanced (4-7%) by ultraviolet irradiation due to the hydrated electrons produced by GRSP. Fe(II) ions, persistent free radicals, and oxygen-containing functional groups on the GRSP surface as electron donors participated in the reduction of Cr(VI) under dark condition. Moreover, Cr(III) was mainly adsorbed on the -COOH groups of GRSP via electrostatic interactions. Based on 2D correlation spectroscopy, the preferential adsorption occurred on the GRSP surface for Cr(VI) in the sequential order of CO → COO- → O-H → C-O. This work provides new insights into the Cr(VI) adsorption and reduction mechanism by GRSP. Overall, GRSP can serve as a natural iron-organic carbon for the photo-reduction of Cr(VI) pollution in environments.

Sequestration of strontium, nickel, and cadmium on glomalin-related soil protein: Interfacial behaviors and ecological functions.

Glomalin-related soil protein (GRSP) is a widespread recalcitrant soil protein complex that promotes the immobilization of metals in soils. Herein, we combined indoor simulation and field investigation to reveal the interfacial behaviors and ecological functions of GRSP to the three typical metals (Sr(II), Ni(II), and Cd(II)). The kinetic and isotherm data suggested that GRSP had a strong ability to adsorb the metals, which was closely related to the Hard-Soft-Acid-Base theory and the film diffusion mechanisms. Regarding environmental factors, the higher solution pH was beneficial to the adsorption of the metals onto GRSP, while the adsorption capacity decreased at lower or higher salinity due to the salting-out and Na+ competition effects. Moreover, Sr(II), Ni(II), and Cd(II) showed competitive adsorption onto GRSP, which was associated with the spatial site resistance effect. By comparing the retention factors of seven natural and artificial particles, GRSP had elevated distribution coefficients in high metal concentration, while its retention factors showed a relatively lower decrease, suggesting that GRSP had excellent buffer performance for a potential metal pollution emergency. Through the continental-scale coastal regions investigation, GRSP sequestered 1.05-3.11 µmol/g Ni, 0.31-1.49 µmol/g Sr, and 0.01-0.06 µmol/g Cd with 0.54-0.91 % of the sediment mass, demonstrating its strong ability to adsorb the metals. Therefore, we advocate that GRSP, as a recalcitrant protein complex, can be considered an effective tool for buffering capacity of metal pollution and environmental capacity within coastal wetlands.