Molecular transformation of petroleum compounds by hydroxyl radicals produced upon oxidation of reduced nontronite

被引：10

作者：

Liu, Yuan ^{[1
,2
]}

Zhang, Yahe ^{[3
]}

Chen, Guo ^{[4
]}

Li, Yang ^{[1
,2
]}

Zeng, Qiang ^{[1
,2
]}

Hu, Jinglong ^{[1
,2
]}

Hu, Dafu ^{[1
,2
]}

Dong, Hailiang ^{[1
,2
]}

机构：

[1] China Univ Geosci, Ctr Geomicrobiol & Biogeochem Res, State Key Lab Biogeol & Environm Geol, Beijing 100083, Peoples R China

[2] China Univ Geosci, Sch Earth Sci & Resources, Beijing 100083, Peoples R China

[3] China Univ Petr, State Key Lab Heavy Oil Proc, Beijing 102249, Peoples R China

[4] Yangtze Univ, Coll Resources & Environm, Wuhan 430070, Peoples R China

来源：

GEOCHIMICA ET COSMOCHIMICA ACTA | 2024年 / 371卷

基金：

中国博士后科学基金;

关键词：

Nontronite; Petroleum compounds; Hydroxyl radicals; Reactivity; Oxidation mechanisms; DISSOLVED ORGANIC-MATTER; POLAR NSO COMPOUNDS; CRUDE-OIL; RATE CONSTANTS; CONTAMINATED SOIL; ELECTRON-TRANSFER; BIODEGRADED OILS; FENTONS REAGENT; CATALYZES H2O2; CLAY-MINERALS;

D O I：

10.1016/j.gca.2024.02.019

中图分类号：

P3 [地球物理学]; P59 [地球化学];

学科分类号：

0708 ; 070902 ;

摘要：

At redox interfaces, the interaction between oxygen and structural Fe(II) in minerals produces hydroxyl radicals (SOH); however, the specific reactivity and mechanisms of oxidation of complex petroleum compounds by SOH remain poorly understood. This study investigates the interaction mechanisms between SOH generated from reduced nontronite, an Fe -rich clay mineral (NAu-2), and petroleum compounds by employing a suite of wet chemistry, gas chromatography mass spectrometry and Fourier transform -ion cyclotron resonance -mass spectrometry, as well as theoretical calculations. The results showed that the intrinsic structure, composition, solubility, and adsorption of petroleum molecules onto reduced NAu-2 significantly influenced their reactivity with SOH. Specifically, the aromatic fraction of a crude oil sample exerted a minimal influence on the oxidation rate of structural Fe(II) in reduced NAu-2, but enhanced the production of SOH by generating environmentally persistent free radicals. SOH reacted more with water-soluble dissolved organic matter from oil compared to polar compounds. The newly generated molecules by SOH exhibited a preference for the insoluble (polar) phase. The oxidation of petroleum hydrocarbons by SOH was mediated through hydrogen atom abstraction and radical adduct formation, followed by dehydrogenation, hydroxylation, and carboxylation reactions. Consequently, the abundance of oxygen -containing compounds in polar compounds increased. However, specific oxidation pathways differed depending on the nature of petroleum compounds. Our results provide insights that oxidation of petroleum compounds by SOH is vital for mitigating the negative impacts from hydrocarbon contamination and for evaluating the role of these processes in the carbon cycle in redox-active environments.

引用

页码：31 / 51

页数：21

共 109 条

[1] Identification of enzymes involved in anaerobic benzene degradation by a strictly anaerobic iron-reducing enrichment culture [J].

Abu Laban, Nidal ;

Selesi, Drazenka ;

Rattei, Thomas ;

Tischler, Patrick ;

Meckenstock, Rainer U. .

ENVIRONMENTAL MICROBIOLOGY, 2010, 12 (10) :2783-2796

[2] Improvements to the quantitative assay of nonrefractory minerals for Fe(II) and total Fe using 1,10-phenanthroline [J].

Amonette, JE ;

Templeton, JC .

CLAYS AND CLAY MINERALS, 1998, 46 (01) :51-62

[3]

Boll M., 2020, Anaerobic Utilization of Hydrocarbons, Oils, and Lipids, P3, DOI [DOI 10.1007/978-3-319-50391-22, 10.1007/978-3-319-50391-2_2, DOI 10.1007/978-3-319-50391-2_2]

[4] CRITICAL-REVIEW OF RATE CONSTANTS FOR REACTIONS OF HYDRATED ELECTRONS, HYDROGEN-ATOMS AND HYDROXYL RADICALS (.OH/.O-) IN AQUEOUS-SOLUTION [J].