Crucial roles of soil inherent Fe-bearing minerals in enhanced Cr(VI) reduction by biochar: The electronegativity neutralization and electron transfer mediation.

Biochar has been used for soil Cr(VI) remediation in the last decade due to its enriched redox functional groups and good electrochemical properties. However, the role of soil inherent Fe-bearing minerals during the reduction of Cr(VI) has been largely overlooked. In this study, biochar with different electron-donating capacities (EDCs) was produced at 400 °C (BC400) and 700 °C (BC700), and their performance for Cr(VI) reduction in soils with varied properties (e.g., Fe content) was investigated. The addition of BC400 caused around 14.2-36.0 mg g-1 Cr(VI) reduction after two weeks of incubation in red soil, paddy soil, loess soil, and fluvo-aquic soil, while a less Cr(VI) was reduced by BC700 (2.57-16.7 mg g-1) with smaller EDCs. The Cr(VI) reduction by both biochars in different soils was closely related to Fe content (R2 = 0.93-0.98), so red soil with the richest Fe (14.8% > 1.79-3.49%) showed the best reduction capability, and the removal of soil free Fe oxides (e.g., hematite) resulted in 71.9% decrease of Cr(VI) reduction by BC400. On one hand, Fe-bearing minerals could increase the soil acidity, neutralize the surface negative charge of biochar, enhance the contact between Cr(VI) and biochar, and thus facilitate the direct Cr(VI) reduction by biochar in soils. On the other hand, Fe-bearing minerals could also facilitate the indirect Cr(VI) reduction by mediating the electron from biochar to Cr(VI) with the cyclic transformation of Fe(II)/Fe(III). This study demonstrates the key role of soil Fe-bearing minerals in Cr(VI) reduction by biochar, which advances our understanding on the biochar-based remediation mechanism of Cr(VI)-contaminated soils.

Mineralogical transformation of arsenic at different copper smelting workshops: The impact on arsenic bioaccessibility.

Soil arsenic (As) contamination associated with the demolition of smelting plants has received increasing attention. Soil As can source from different industrial processes, and also participate in soil weathering, making its speciation rather complex. This study combined the usage of chemical sequential extraction and advanced spectroscopic techniques, e.g., time of flight secondary ion mass spectrometry (ToF-SIMS), to investigate the mineralogical transformation of soil As at different processing sites from a typical copper smelting plant in China. Results showed that the stability of arsenic species decreased following the processes of storage, smelting, and flue gas treatment. Arsenic in the warehouse area was incorporated into pyrite (FeS2) as well as its secondary minerals such as jarosite (KFe3(SO4)2(OH)6). At the smelting area, a large proportion of As was adsorbed by iron oxides from smelting slags, while some As existed in stable forms like orpiment (As2S3). At the acid-making area, more than half of As was adsorbed on amorphous iron oxides, and some were adsorbed on the flue gas desulfurization gypsum. More importantly, over 86% of the As belonged to non-specifically and specifically adsorbed fractions was found to be bioaccessible, highlighting the gypsum-adsorbed As one of the most hazardous species in smelting plant soils. Our findings indicated the importance of iron oxides in As retention and suggested the potential health risk of gypsum-adsorbed As. Such detailed knowledge of As speciation and bioaccessibility is vital for the management and remediation of As-contaminated soils in smelting plants.

Mesoporous ball-milling iron-loaded biochar for enhanced sorption of reactive red: Performance and mechanisms.

In order to solve the low sorption capacity of pristine biochar for anionic pollutants, e.g., reactive red 120 (RR120), a novel mesoporous Fe-biochar composite was fabricated in this study by combination of Fe-loading and ball-milling methods. The ball-milling Fe-biochar composite could effectively remove RR120 by up to 90.1 mg g-1 at pH of 7.5, and slightly alkaline condition was preferred. Adsorption kinetics showed that ball-milling Fe-biochar composite could quickly sorb RR120 with the rate constant (k2) of 2.07 g mg-1 min-1 (pH = 7.5). Positive surface charge and large surface area were responsible for the outstanding removal performance of RR120 by ball-milling Fe-biochar composite: (1) The adscititious Fe would be converted to ß-FeOOH during pyrolysis, which significantly improved the zeta potential of biochar and thus facilitated the electrostatic adsorption for RR120, which contributed to 42.3% and 85.5% at pH of 3 and 7.5, respectively; (2) Ball-milling effectively increased the specific surface area and uniformed the pore size distribution, which could provide more sorption sites and expedite the diffusion of RR120 molecules, shortening the time from several hours to less than 15 min. Findings of this study not only provide a feasible modification method for biochar to adsorb anionic pollutants efficiently and rapidly, but also help to reveal the roles of Fe-loading and ball-milling in enhancing adsorption capacity.