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Shi, Qiantao

Publications and source records attributed to Shi, Qiantao.

9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. In conclusion, these findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Mechanistic insights into Cr(VI) removal by a combination of zero-valent iron and pyrite

Recent studies have revealed that a combination of zero-valent iron (ZVI) and pyrite (FeS 2 ) can effectively remove (Cr(VI)) from water, but the reasons behind this synergistic effect are still unclear. Our batch experiments showed that dissolved oxygen (DO) is a critical factor in the improved removal of Cr(VI) by ZVI and pyrite. When 0.08 g/L pyrite was combined with 0.5 g/L ZVI in the presence of DO, total Cr was reduced from 10 mg/L to 0.02 mg/L within 6 h. Conversely, in the absence of DO, total Cr was only reduced to 5.6 mg/L. DO oxidation of pyrite produced protons that promote ZVI corrosion, and mixing pyrite with water creates dissolved sulfide, which also contributes to the improved removal of Cr(VI). Here, electron microscopy images and X-ray absorption near edge structure analyses revealed that the presence of dissolved sulfide led to the formation of ferrous sulfide precipitates on the ZVI surface, preventing the formation of a passivating layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanisms of phosphate removal by Micron-Scale Zero-Valent iron

Extensive studies have been carried out on phosphate removal by zero valent iron (ZVI). Different mechanisms of phosphate removal by ZVI such as phosphate adsorption and precipitation of ferric phosphate and vivianite (Fe 3 (PO 4 ) 2 ·8H 2 O) have been reported. In this study, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray powder diffraction (XRD), and X-ray absorption near edge spectroscopy (XANES) were used to elucidate the mechanisms of phosphate removal by micron-scale zero-valent (mZVI). Time-series ATR-FTIR analysis revealed that phosphate was removed by ZVI in two steps: a) adsorption of phosphate in the first 3 days, and b) slow conversion of the adsorbed phosphate into the precipitated form in 6 days. XRD and XANES analysis determined that iron oxides, ferric ion, and ZVI with oxide layer inhibited the formation of vivianite, resulting in the formation of phosphate precipitates, such as H 2 Fe(II)P 2 O 7 . The results suggested that phosphate is removed by ZVI mainly through precipitation under aerobic conditions. In conclusion, the knowledge gained in this study improves the fundamental understanding of the phosphate removal processes via ZVI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS

In this article, a novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N 2 , air, or O 2 gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O 2 -purging DNAN degradation rate was slightly enhanced, but most notably O 2 significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

54 ENVIRONMENTAL SCIENCES↗