Ozonolysis of α-PINENE, β-PINENE, d- and l-Turpentine Oil Studied by Chirooptical Methods; Some Implications on the Atmospheric Chemistry of Biogenic Volatile Organic Compounds

Abstract

The main constituents of biogenic volatile organic compounds (BVOC) released in the atmosphere from vegetation are terpenes. The most common terpenes are α-pinene and β-pinene. These molecules react with ozone, forming oxidized derivatives which have low vapor pressure and which nucleate into secondary organic aerosol (SOA). Such aerosol-forming reactions have been simulated in the gas phase on laboratory scale with the visualization of the formation of SOA. Electronic absorption spectroscopy shows that the UV peak of pinenes at 205 nm is shifted to 225 nm during and after ozonolysis and is accompanied by a series of spectral features in the near infrared region (between 850 nm and 1100 nm). Optical rotatory dispersion (ORD) spectra were recorded on pure β(+)pinene and β(−)pinene. After ozonolysis β-pinene enantiomers are converted into nopinone enantiomers. The ORD spectra of both (−)nopinone and (+)nopinone respectively were recorded. The former showed a peak at 453 nm, an inflection point at 430 nm and a trough at 405 nm. The ORD spectrum of (−)-nopinone appears completely symmetrical to that of (+)nopinone. Thus, ORD spectroscopy can distinguish between BVOC and oxidized BVOC quite easily at least in the case of β-pinene. The ORD spectra of α-pinene enantiomers are different from those of β-pinene enantiomers and although the ORD spectra of ozonized α-pinene are not easily distinguishable from those of the primary compounds, they are completely different from those of ozonized β-pinene enantiomers. A reasonable natural model of BVOC is offered by l- and d-turpentine oil whose composition reflects that of the BVOC from conifer forests. The ORD spectra of ozonized l- and d-turpentine has permitted to distinguish between the levorotatory and dextrorotatory oxidation products and showing the ketone peak at about 367–380 nm, thus permitting in a real model to distinguish between primary BVOC (turpentine) and oxidized BVOC (or SOA) corresponding to ozonized turpentine. It has been proposed that ORD spectra in the gas phase could be used to detect chiral BVOC and oxidized chiral BVOC.