Cations facilitate sulfidation of zero-valent iron by elemental sulfur: Mechanism and dechlorination application.

The solid-solid reaction of microscale zero-valent iron (mZVI) with elemental sulfur (S0) in water can form sulfidated mZVI (S-mZVI) with high reactivity and selectivity. However, the inherent passivation layer of mZVI hinders the sulfidation. In this study, we demonstrate that ionic solutions of Me-chloride (Me: Mg2+, Ca2+, K+, Na+ and Fe2+) can accelerate the sulfidation of mZVI by S0. The S0 with S/Fe molar ratio of 0.1 was fully reacted with mZVI in all solutions to form unevenly distributed FeS species on S-mZVIs as confirmed by SEM-EDX and XANES characterization. The cations depassivated the mZVI surface by driving the proton release from the surface site (FeOH) and resulting in localized acidification. The probe reaction test (tetrachloride dechlorination) and open circuit potential (EOCP) measurement demonstrated that Mg2+ was most efficient in depassivating the mZVI and therefore promoting sulfidation. The decrease of surface proton for hydrogenolysis on the S-mZVI synthesized in MgCl2 solution also inhibited the formation of cis-1,2-dichloroethylene by 14-79% compared to other S-mZVIs during trichloroethylene dechlorination. In addition, the synthesized S-mZVIs exhibited the highest reduction capacity reported so far. These findings provide a theoretical basis for the facile on-site sulfidation of mZVI by S0 with cation-rich natural waters for sustainable remediation of contaminated sites.

Reductive dechlorination of chlorinated ethenes by ball milled and mechanochemically sulfidated microscale zero valent iron: A comparative study.

Ball milling is an effective technique to not only activate and reduce the size of commercial microscale zero valent iron (mZVI) but also to mechanochemically sulfidate mZVI. Yet, little is known about the difference between how chlorinated ethenes (CEs) interact with ball milled mZVI (mZVIbm) and mechanochemically sulfidated mZVI (S-mZVIbm). We show that simple ball milling exposed the active Fe0 sites, while mechanochemical sulfidation diminished Fe0 sites and meanwhile increased S2- sites. Mechanochemical sulfidation with [S/Fe]dosed increased from 0 to 0.20 promoted the particle reactivity most for TCE dechlorination (∼14-fold), followed by PCE and 1,1-DCE while it diminished the reactivity for trans-DCE (∼0.4-fold), cis-DCE (∼0.02-fold) and VC (∼0.002-fold) compared to simple ball milling. Sulfidation also improved the electron efficiency of CE dechlorination, except for cis-DCE and VC. The kSA of cis-DCE, VC and trans-DCE dechlorination positively correlated with surface Fe0 content, suggesting their dechlorination was mainly mediated by Fe0 site or reactive atomic hydrogen. The kSA of TCE dechlorination positively correlated with surface S2- content and the dechlorination mainly occurred on S2- sites via direct electron transfer. Increased sulfidation favored direct electron transfer mechanism. The kSA of PCE and 1,1-DCE was not dependent on either parameter and their dechlorination was equally achieved through either mechanism.

Sulfidation of Zero-Valent Iron by Direct Reaction with Elemental Sulfur in Water: Efficiencies, Mechanism, and Dechlorination of Trichloroethylene.

Sulfidation can enhance both the reactivity and selectivity (i.e., electron efficiency, εe) of zero-valent iron (ZVI) in contaminant removal, which may make this technology cost-effective for a wider range of water treatment applications. However, current sulfidation methods involve either hazardous or unstable sulfidation agents (e.g., Na2S, Na2S2O3, and Na2S2O4) or energy-intensive preparations (e.g., mechanochemical sulfidation with elemental sulfur). In this study, we demonstrate that very efficient sulfidation of microscale ZVI (mZVI) can be achieved at all S/Fe molar ratios (∼100% sulfidation efficiency, εs) simply by direct reaction between elemental sulfur (S0) and ZVI in an aqueous suspension at ambient temperature. In comparison, the εs values obtained using Na2S, Na2S2O3, or Na2S2O4 as the sulfidation agents were only ∼23, ∼75, and ∼38%, respectively. The sulfidated mZVI produced using the new method reacts with trichloroethylene (TCE) with very high rates and electron efficiencies: rate constants and electron efficiencies were 800- and 79-fold higher than those of the unsulfidated mZVI. The enhanced performance of this material, together with the operational advantages of S0 for sulfidation (including safety, stability, and cost), may make it a desirable product for full-scale engineering applications.

Sulfidation mitigates the passivation of zero valent iron at alkaline pHs: Experimental evidences and mechanism.

Groundwater pH is one of the most important geochemical parameters in controlling the interfacial reactions of zero-valent iron (ZVI) with water and contaminants. Ball milled, microscale ZVI (mZVIbm) efficiently dechlorinated TCE at initial stage (<24 h) at pH 6-7 but got passivated at later stage due to pH rise caused by iron corrosion. At pH > 9, mZVIbm almost completely lost its reactivity. In contrast, ball milled, sulfidated microscale ZVI (S-mZVIbm) didn't experience any reactivity loss during the whole reaction stage across pH 6-10 and could efficiently dechlorinate TCE at pH 10 with a reaction rate of 0.03 h-1. Increasing pH from 6 to 9 also enhanced electron utilization efficiency from 0.95% to 5.3%, and from 3.2% to 22%, for mZVIbm and S-mZVIbm, respectively. SEM images of the reacted particles showed that the corrosion product layer on S-mZVIbm had a puffy/porous structure while that on mZVIbm was dense, which may account for the mitigated passivation of S-mZVIbm under alkaline pHs. Density functional theory calculations show that covered S atoms on the Fe(100) surface weaken the interactions of H2O molecules with Fe surfaces, which renders the sulfidated Fe surface inefficient for H2O dissociation and resistant to surface passivation. The observation from this study provides important implication that natural sulfidation of ZVI may largely contribute to the long-term (>10 years) efficiency of TCE decontamination by permeable reactive barriers with pore water pH above 9.