title: Peroxidase-catalyzed oxidative coupling of phenols in the presence of geosorbents: rates of non-extractable product formation.
abstract: Oxidative coupling processes in subsurface systems comprise a form of natural contaminant attenuation in which hydroxylated aromatic compounds (HACs) are incorporated into soil/sediment organic matter matrices. Here we describe the oxidative coupling of phenol catalyzed by horseradish peroxidase (HRP) in systems containing two geosorbents having organic matter of different composition; specifically Chelsea soil, a near-surface geologically young soil having a predominantly humic-type soil/sediment organic matter (SOM) matrix, and Lachine shale, a diagenetically older natural material having a predominantly kerogen-type SOM matrix. It was found that each of these two different types of natural geosorbents increased the formation of non-extractable coupling products (NEPs) over that which occurred in solids-free systems. The extent of coupling was higher in the systems containing humic-type Chelsea SOM than in those containing kerogen-type Lachine SOM. It was observed that HRP inactivation by free radical attack was significantly reduced in the presence of each geosorbent. A rate model was developed to facilitate quantitative evaluation and mechanistic interpretation of such coupling processes. Experimental rate measurements revealed thatthe greater extent of reaction observed in the presence of Chelsea soil than in the presence of Lachine shale can be attributed to two factors: (i) more effective protection of HRP from inactivation by the Chelsea SOM and (ii) the greater reactivity of Chelsea SOM with respect to cross-coupling. Interrelationships among enzyme protection, cross-coupling reactivity, and SOM chemistry are discussed.
authors.affiliation: Environmental and Water Resources Engineering, Department of Chemical Engineering, The University of Michigan, Ann Arbor 48109-2125, USA.
authors.forename: Qingguo
authors.initials: Q
authors.lastname: Huang
authors.forename: Hildegarde
authors.initials: H
authors.lastname: Selig
authors.forename: Walter J
authors.initials: WJ
authors.lastname: Weber
mesh_terms: D000327:Adsorption; D006735:Horseradish Peroxidase / Q000494:pharmacology; D006812:Humic Substances / Q000737:chemistry; D008956:Models, Chemical; D009930:Organic Chemicals; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D012989:Soil Pollutants / Q000032:analysis*
chemical_list: D006812:Humic Substances; D009930:Organic Chemicals; D010636:Phenols; D012989:Soil Pollutants; D006735:Horseradish Peroxidase