REMEDIATION OF PER- AND POLYFLUOROALKYL SUBSTANCES AND COMINGLED CHLORINATED SOLVENTS USING REDUCED GRAPHENE OXIDE/NANOSCALE ZERO-VALENT IRON

Author

Sushmita Regmi, Southern Illinois University CarbondaleFollow

Date of Award

8-1-2022

Degree Name

Master of Science

Department

Civil Engineering

First Advisor

Liu, Jia

Abstract

The lack of biodegradability of PFAS, or per- and polyfluoroalkyl substances, is due to the presence of many strong carbon-fluorine bonds. Two common PFAS that are found in the environment are perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). This work first studied an innovative pathway for PFAS removal through the adsorption of PFOA and PFOS (pre-concentrating the contaminants) by nanoscale zero-valent iron/reduced graphene oxide (rGO-nZVI) and their subsequent degradation via photocatalysis under UVC light. The GO that was later reduced in nanohybrid production was made utilizing a modified Hummer’s method. The rGO-nZVI nanohybrid was prepared for the first time via thermal reduction at high temperatures. Additionally, the nanohybrid was prepared using the wet chemistry method for comparison. LC/MS/MS analysis was conducted to determine the adsorption efficiencies for PFOA and PFOS using the nanohybrids and their successive removal under UVC light. Chlorinated hydrocarbons are another group of contaminants of concern that should be removed from the subsurface due to their harmful effects. In this study, a more complex mixture of the contaminants including PFAS and chlorinated hydrocarbons was investigated, which is usually found in the superfund and other contaminated sites. Considering the effectiveness of nZVI to remove chlorinated hydrocarbons from the subsurface, engineered nZVI coupled with rGO was utilized to enhance the removal efficiency of the mixture of contaminants, i.e., PFAS comingled with chlorinated hydrocarbons. The synthesized rGO-nZVI nanoparticle showed high adsorption efficiencies for both PFOA and PFOS, i.e., removal of 55.3%, 98.2%, and >99.9% of PFOA of 10, 1, and 0.1 mg/L, and 94.9%, 97.6%, and 85.0% of PFOS of 10, 1, and 0.1 mg/L, respectively, in 3 h. Later degradation of pre-concentrated PFAS under UVC light was also achieved. Using extracted rGO-nZVI, 55.1%, 77.6% of preconcentrated PFOS was degraded starting from 10, and 1 mg/L of initial concentrations before adsorption in the photoreactor at the end of 24 h. In comparison, 68.5% and 47.2% of PFOS and PFOA (starting from 1 mg/L each) was degraded, respectively, using rGO-nZVI directly under UVC light after 24 h. Moreover, it was found that rGO-nZVI had high adsorption capacity of 69.4% and 68.7% respectively for TCE and PFOA in a mixture of these contaminants. Under UVC irradiation, the preconcentrated mixture of TCE and PFOA were both degraded to below the detection limit in 21 h. It was also found that PFOA concentration dropped by 64.3% at 5 h and by 88.7% at 24 h by fresh rGO-nZVI in presence of 10 mg/L TCE. Short-chained PFCAs like PFHpA and PFHxA were found as the intermediates for PFOA degradation using rGO-nZVI under UVC light. Also, under UVC irradiation of a mixture of TCE and PFOA, TCE degradation was supported by the formation of intermediates during the reaction. Because of its composition, photocatalytic activity, large surface area, magnetic properties, and environmental friendliness, the thermal reduced rGO-nZVI particle demonstrated its potential to successfully remove PFAS and comingled chlorinated hydrocarbon from pre-concentration followed by degradation under UVC light. The nanohybrid is promising to be used to repair PFAS-contaminated water bodies.