Sulfidation extent of nanoscale zerovalent iron controls selectivity and reactivity with mixed chlorinated hydrocarbons in natural groundwater.

Sulfidated nanoscale zerovalent iron (S-nZVI) exhibits low anoxic oxidation and high reactivity towards many chlorinated hydrocarbons (CHCs). However, nothing is known about S-nZVI reactivity once exposed to complex CHC mixtures, a common feature of CHC plumes in the environment. Here, three S-nZVI materials with varying iron sulfide (mackinawite, FeSm) shell thickness and crystallinity were exposed to groundwater containing a complex mixture of chlorinated ethenes, ethanes, and methanes. CHC removal trends yielded pseudo-first order rate constants (kobs) that decreased in the order: trichloroethene > trans-dicloroethene > 1,1-dichlorethene > trichloromethane > tetrachloroethene > cis-dichloroethene > 1,1,2-trichloroethane, for all S-nZVI materials. These kobs trends showed no correlation with CHC reduction potentials based on their lowest unoccupied molecular orbital energies (ELUMO) but absolute values were affected by the FeSm shell thickness and crystallinity. In comparison, nZVI reacted with the same CHCs groundwater, yielded kobs that linearly correlated with CHC ELUMO values (R2 = 0.94) and that were lower than S-nZVI kobs. The CHC selectivity induced by sulfidation treatment is explained by FeSm surface sites having specific binding affinities towards some CHCs, while others require access to the metallic iron core. These new insights help advance S-nZVI synthesis strategies to fit specific CHC treatment scenarios.

Effects of common groundwater ions on the transformation and reactivity of sulfidized nanoscale zerovalent iron.

Sulfidized nanoscale zerovalent iron (S-nZVI) is an Fe-based reactant widely studied for its potential use for groundwater remediation. S-nZVI reactivity has been widely investigated testing various contaminants in various water matrices, but studies on S-nZVI corrosion behaviour and reactivity upon exposure to complex groundwater chemistries are limited. Here, we show that anoxic aging of S-nZVI for 7 days in the absence and presence of key groundwater solutes (i.e., Cl-, SO42-, Mg2+, Ca2+, HCO3-, CO32-, NO3-, or HPO42-) impacts Fe0 corrosion extent, corrosion product and reduction rates with trichloroethene (TCE). White rust was the dominant corrosion product in ultrapure water and in SO42-, Cl-, Mg2+ or Ca2+ solutions; green rust and/or chukanovite formed in HCO3- and CO32- solutions; magnetite, formed in NO3- solutions and vivianite in HPO42- solutions. The aged S-nZVI materials expectedly showed lower reactivities with TCE compared to unaged S-nZVI, with reaction rates mainly controlled by ion concentration, Fe0 corrosion extent, type(s) of corrosion product, and solution pH. Comparison of these results to observations in two types of groundwaters, one from a carbonate-rich aquifer and one from a marine intruded aquifer, showed that S-nZVI corrosion products are likely controlled by the dominant GW solutes, while reactivity with TCE is generally lower than expected, due to the multitude of ion effects. Overall, these results highlight that S-nZVI corrosion behaviour in GW can be manifold, with varied impact on its reactivity. Thus, testing of S-nZVI stability and reactivity under expected field conditions is key to understand its longevity in remediation applications.

Hydrotalcite stability during long-term exposure to natural environmental conditions.

Hydrotalcite-like compounds are a group of layered double hydroxides widely studied as sorbents to remove organic and inorganic contaminants under laboratory conditions. This study is a proof-of-concept of the long-term fate of hydrotalcite compounds under natural environmental conditions, to bridge the gap between laboratory studies and their field application as sorbents. Hydrotalcite (HT) with intercalated carbonate species (HT-CO3) and dodecyl sulphate (HT-DS) were synthesised and placed in two groundwater monitoring wells in Denmark, one contaminated with chlorinated hydrocarbons and another with uncontaminated groundwater. To assess the structural and surface compositional changes of hydrotalcite compounds upon prolonged exposure to groundwater, the material was analysed with powder X-ray diffraction (PXRD), Fourier-transformed infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results showed that the stability and dissolution behaviour of hydrotalcite compounds under groundwater conditions depended on the intercalated anion (CO32- > DS) and groundwater dynamics (static flow > dynamic flow), while the hydrotalcite aggregate size only had a minor effect. Groundwater geochemistry influenced the precipitation of insoluble species (CaCO3, and adsorbed sulphate) on the hydrotalcite surface. The instability of hydrotalcite compounds, especially in the case of HT-DS, may constitute a significant limiting factor on their future application as sorbents under dynamic flow conditions.

Sorption of chlorinated hydrocarbons from synthetic and natural groundwater by organo-hydrotalcites: Towards their applications as remediation nanoparticles.

Chlorinated hydrocarbons (CHCs) are recalcitrant compounds frequently found as contaminants in groundwater. Hydrotalcites (HT) have emerged as promising sorbents due to their tunable properties and anion exchange capacity. Here, two types of organo-HT were synthesized, via coprecipitation, by intercalation of two different anionic surfactants, sodium dodecyl sulfate and sodium 1-dodecane sulfonate. These compounds were first characterized by a suite of techniques to quantify surfactant intercalation and to evaluate their physico-chemical properties. Next, the sorption affinity of these organo-HT towards a suite of CHCs was tested under various conditions, including interlayer surfactant type, single and multiple CHCs systems, and different water chemistry (pH, ionic composition). Sorption coefficients (Kd) and organic-matter-normalized partition coefficient (Kom) derived from linear sorption isotherms for individual CHC were inversely correlated to their hydrophobicity in the order of: tetrachloroethylene > tetrachloromethane > trichloroethylene> 1,1,2-trichloroethane > trichloromethane. Kom values were further affected by the organo-HT drying process. In contrast, varying water chemistry and pH, and the co-existence of multiple CHCs had little effect on Kom values, indicating that competition between CHCs and ionic strength have a marginal effect on the sorption affinity. The inverse linear relationship between CHC hydrophobicity and Kom is shown to be a suitable tool to predict organo-HT's sorption efficiency in complex CHCs contaminated groundwaters. Overall, organo-HT's might be used as potential sorbents for ex situ treatment of CHCs in groundwater.