Abstract

Abstract. Volatile organic compounds like furan and its derivatives are important for atmospheric properties and reactions. In this work the known abiotic formation of furan from catechol under Fenton-like conditions with Fe3+ sulfate was revised by the use of a bispidine Fe2+ complex as a model compound for iron with well-known characteristics. While total yields were comparable to those with the Fe3+ salt, the bispidine Fe2+ complex is a better catalyst as the turnover numbers of the active iron species were higher. Additionally, the role of iron and pH is discussed in relation to furan formation from model compounds and in natural sediment and water samples collected from the Dead Sea and several salt lakes in Western Australia. Various alkylated furans and even traces of halogenated furans (3-chlorofuran and 3-bromofuran) were found in some Australian samples. 3-chlorofuran was found in three sediments and four water samples, whereas 3-bromofuran was detected in three water samples. Further, the emission of furans is compared to the abundance of several possible precursors such as isoprene and aromatic hydrocarbons as well as to the related thiophenes. It is deduced that the emissions of volatile organic compounds such as furans contribute to the formation of ultra-fine particles in the vicinity of salt lakes and are important for the local climate.

Highlights

  • Furans are heterocyclic aromatic compounds with a fivemembered ring consisting of four carbons and one oxygen atom and are closely related to the sulfur-containing thiophenes

  • While the bispidine Fe2+ complex is stabilised in solution by its ligands, the Fe3+ salt is susceptible to precipitation and is removed from the reaction cycle. This cycle includes the oxidation of Fe2+ by H2O2 in the Fenton reaction to Fe3+ (Remucal and Sedlak, 2011) and forming a highly reactive OH radical and a hydroxyl anion (Haber and Weiss, 1932)

  • Fe3+ on the other hand can be either reduced by catechol, which is a one to two electron donor, or by the Fenton-like reaction with H2O2 yielding in both cases Fe2+

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Summary

Introduction

Furans are heterocyclic aromatic compounds with a fivemembered ring consisting of four carbons and one oxygen atom and are closely related to the sulfur-containing thiophenes. Bispidine complexes have a defined coordination sphere due to the rigid adamantane backbone (Comba et al, 2010) and are well studied in their coordination with catechol (Comba et al, 2011) as well as their redox reaction with hydrogen peroxide (Bukowski et al, 2006). Aside from that, such chelating agent can be used to enhance the reaction and to impede side reactions

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