Abstract

In this study, batch experiments were carried out to investigate the effectiveness of persulfate (PS) as an oxidant agent to remediate benzene, toluene, ethylbenzene, and xylenes (BTEX) in saline environments and at high water temperatures (30 °C). This hydrological setting is quite common in contaminated groundwater aquifers in Middle Eastern countries. In general, increasing the system temperature from 10 to 30 °C greatly enhanced the effectiveness of PS, and resulted in a faster oxidation rate for the target contaminants. When PS was added to the reactor at 30 °C, the targeted contaminants were almost completely oxidized over a 98-day reaction period. During the chemical oxidation of the BTEX, carbon and hydrogen isotope fractionations were monitored and utilized as potential proof of contaminant degradation. The calculated carbon-enrichment values were −1.9‰ for benzene, −1.5‰ for ethylbenzene and toluene, −0.4‰ for ρ,m-xylene, and −1.4‰ for o-xylene, while the hydrogen enrichment values were −9.5‰, −6.8‰, −2.1‰, −6.9‰, and −9.1‰, respectively. In comparison with other processes, the hydrogen and carbon isotope fractionations during the chemical oxidation by PS were smaller than the isotope fractionations resulting from sulfate reduction and denitrification. This observation demonstrates the differences in the transformation pathways and isotope fractionations when compounds undergo chemical oxidation or biodegradation. The distinct trend observed on the dual isotope plot (Δδ13C vs. Δδ2H) suggests that compound-specific isotope analysis can be utilized to monitor the chemical oxidation of BTEX by PS, and to distinguish treatment zones where PS and biodegradation technologies are applied simultaneously.

Highlights

  • Introduction iationsIn-situ chemical oxidation (ISCO) is a promising methodology for the remediation of petroleum hydrocarbons due to its relative inexpensiveness, simple preparation of treatment solutions, and the ability to degrade contaminants in place [1]

  • The Initial volatile organic compounds (VOCs) analyses showed that the water samples contain 82.6 mg/L of BTEX, 2.9 mg/L of Trimethylbenzenes, and 0.3 mg/L of naphthalene

  • This data indicates that BTEX accounts for about 96% of the total petroleum hydrocarbons and were chosen as representative compounds

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Summary

Introduction

In-situ chemical oxidation (ISCO) is a promising methodology for the remediation of petroleum hydrocarbons due to its relative inexpensiveness, simple preparation of treatment solutions, and the ability to degrade contaminants in place [1]. ISCO technology involves the reduction of the contaminant mass by injecting chemical oxidants into the vadose or saturated zone. In the past few decades, several aqueous oxidants (e.g., hydrogen peroxide, permanganate, and ozone) have been employed to remediate petroleum hydrocarbons [2,3]. In comparison with other chemical oxidants, persulfate (PS) is more stable than peroxide in the presence of aquifer materials [5], more effective for treating contaminants in the saturated zone than ozone due to its higher aqueous solubility [2], Licensee MDPI, Basel, Switzerland.

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