A comprehensive evaluation of factors affecting the reactivity of FeS towards hexabromocyclododecane diastereoisomers

Abstract

Reactivity of iron sulfide (FeS) towards hexabromocyclododecane (HBCD) was explored under conditions of varying temperature, pH, inorganic ion and dissolved organic matter (DOM) in this study. Results show that the reduction of HBCD by FeS has an activation energy of 29.2 kJ mol−1, suggesting that the rate-limiting step in the reduction was a surface-mediated reaction. The reduction of HBCD by FeS was a highly pH-dependent process. The optimal rate for HBCD reduction by FeS was observed at a pH of 6.2. All the tested inorganic ions suppressed the reduction of HBCD by FeS. XPS analysis confirmed that both Fe(II)-S and bulk S(-II) on FeS surface could be impacted by solution pH and inorganic ions and were responsible for the regulation of HBCD reduction. Some DOMs (i.e., fulvic acid, humic acid, salicylic acid, catechol and sodium dodecyl sulfate) were found to hinder the reduction via competing with HBCD for active sites on FeS surface. However, the presence of 2,2′-bipyridine, triton X-100 and cetyltrimethyl ammonium bromide was able to significantly enhance the rate of HBCD reduction by 5.8, 9.0 and 20 times, respectively. Different factors could influence the reduction efficiency of HBCD diastereoisomers to different extent, but not the reaction orders of HBCD diastereoisomers (α-HBCD < γ-HBCD < β-HBCD). Moreover, FeS could completely remove HBCD diastereoisomers in sediments with multiple factors within 9 d reaction. Our results contribute to give a better understanding on the performance of FeS towards HBCD under real and complex conditions and facilitate the application of FeS in remediation sites.