Atmospheric Degradation of Ecologically Important Biogenic Volatiles: Investigating the Ozonolysis of (E)-ß-Ocimene, Isomers of α and ß-Farnesene, α-Terpinene and 6-Methyl-5-Hepten-2-One, and Their Gas-Phase Products.

Biogenic volatile organic compounds (bVOCs), synthesised by plants, are important mediators of ecological interactions that can also undergo a series of reactions in the atmosphere. Ground-level ozone is a secondary pollutant generated through sunlight-driven reactions between nitrogen oxides (NOx) and VOCs. Its levels have increased since the industrial revolution and reactions involving ozone drive many chemical processes in the troposphere. While ozone precursors often originate in urban areas, winds may carry these hundreds of kilometres, causing ozone formation to also occur in less populated rural regions. Under elevated ozone conditions, ozonolysis of bVOCs can result in quantitative and qualitative changes in the gas phase, reducing the concentrations of certain bVOCs and resulting in the formation of other compounds. Such changes can result in disruption of bVOC-mediated behavioural or ecological interactions. Through a series of gas-phase experiments using Gas Chromatography Mass Spectrometry (GC-MS) and Proton Transfer Reaction Mass Spectrometry (PTR-MS), we investigated the products and their yields from the ozonolysis of a range of ubiquitous bVOCs, which were selected because of their importance in mediating ecological interactions such as pollinator and natural enemy attraction and plant-to-plant communication, namely: (E)-ß-ocimene, isomers of α and ß-farnesene, α-terpinene and 6-methyl-5-hepten-2-one. New products from the ozonolysis of these compounds were identified, and the formation of these compounds is consistent with terpene-ozone oxidation mechanisms. We present the degradation mechanism of our model bVOCs and identify their reaction products. We discuss the potential ecological implications of the degradation of each bVOC and of the formation of reaction products.

Mapping the effects of ozone pollution and mixing on floral odour plumes and their impact on plant-pollinator interactions.

The critical ecological process of animal-mediated pollination is commonly facilitated by odour cues. These odours consist of volatile organic compounds (VOCs), often with short chemical lifetimes, which form the strong concentration gradients necessary for pollinating insects to locate a flower. Atmospheric oxidants, including ozone pollution, may react with and chemically alter these VOCs, impairing the ability of pollinators to locate a flower, and therefore the pollen and nectar on which they feed. However, there is limited mechanistic empirical evidence to explain these processes within an odour plume at temporal and spatial scales relevant to insect navigation and olfaction. We investigated the impact of ozone pollution and turbulent mixing on the fate of four model floral VOCs within odour plumes using a series of controlled experiments in a large wind tunnel. Average rates of chemical degradation of α-terpinene, ß-caryophyllene and 6-methyl-5-hepten-2-one were slightly faster than predicted by literature rate constants, but mostly within uncertainty bounds. Mixing reduced reaction rates by 8-10% in the first 2 m following release. Reaction rates also varied across the plumes, being fastest at plume edges where VOCs and ozone mixed most efficiently and slowest at plume centres. Honeybees were trained to learn a four VOC blend equivalent to the plume released at the wind tunnel source. When subsequently presented with an odour blend representative of that observed 6 m from the source at the centre of the plume, 52% of honeybees recognised the odour, decreasing to 38% at 12 m. When presented with the more degraded blend from the plume edge, recognition decreased to 32% and 10% at 6 and 12 m respectively. Our findings highlight a mechanism by which anthropogenic pollutants can disrupt the VOC cues used in plant-pollinator interactions, which likely impacts on other critical odour-mediated behaviours such as mate attraction.

Esterification of residual palm oil using solid acid catalyst derived from rice husk.

In this study, carbon-silica based acid catalysts derived from rice husks (RH) were successfully synthesised using microwave (MW) technology. The results showed that MW sulphonation produced Sulphur (S) content of 17.2-18.5 times higher than in raw RH. Fourier-transform Infrared Spectroscopy (FTIR) showed peak at 1035 cm-1 which corresponded to O˭S˭O stretching of sulphonic (-SO3H) group. XRD showed sulfonated RH catalysts (SRHCs) have amorphous structure, and through SEM, broadening of the RH voids and also formation of pores is observed. RH600 had the highest surface area of 14.52 m2/g. SRHCs showed high catalytic activity for esterification of oleic acid with methanol with RH600 had the highest initial formation rate (6.33 mmolL-1min-1) and yield (97%). The reusability of the catalyst showed gradually dropped yield of product for every recycle, which might be due to leaching of -SO3H. Finally, esterification of oil recovered from palm oil mill effluent (POME) with methanol achieved a conversion of 87.3% free fatty acids (FFA) into fatty acid methyl esters (FAME).

Recovery of oil from palm oil mill effluent using polypropylene micro/nanofiber.

Residual palm oil that goes into the river untreated can become detrimental to the environment. Residual oil discharge during milling process into palm oil mill effluent (POME) is unavoidable. About 1 wt% of residual oil in POME causes major problems to the mills, in terms of environment, wastewater treatment and economy losses. This paper reports the recovery of residual oil from POME by adsorption on polypropylene micro/nanofiber (PP-MNF) and desorption of oil by hands pressing, and oil extraction from the PP-MNF using solvent and supercritical-CO2 extraction techniques. The characterization of the PP-MNF and the quality of oil extracted were analyzed using analytical instruments. The reusability of the PP-MNF was also investigated. The experimental results showed the adsorption capacity of the PP-MNF was 28.65 g of oil/g of PP-MNF on average using refined palm oil, whilst recovery of oil from POME was 10.93 g of oil/g of PP-MNF. The extraction yield of oil from PP-MNF using hand pressing was 89.62%. The extraction of residual oil from the pressed PP-MNF showed comparable yield between solvent and supercritical CO2 techniques. The quality of recovered oil was similar with the quality of the crude oil, and no trace of polypropylene contamination was detected in the oil recovered. The PP-MNF showed no significant physical change after the extraction process. In conclusion, the PP-MNF has great potential to be used commercially in residual oil recovery from POME.

Study of Pyridine-Mediated Electrochemical Reduction of CO2 to Methanol at High CO2 Pressure.

The recently proposed highly efficient route of pyridine-catalyzed CO2 reduction to methanol was explored on platinum electrodes at high CO2 pressure. At 55 bar (5.5 MPa) of CO2 , the bulk electrolysis in both potentiostatic and galvanostatic regimes resulted in methanol production with Faradaic yields of up to 10 % for the first 5-10 C cm(-2) of charge passed. For longer electrolysis, the methanol concentration failed to increase proportionally and was limited to sub-ppm levels irrespective of biasing conditions and pyridine concentration. This limitation cannot be removed by electrode reactivation and/or pre-electrolysis and appears to be an inherent feature of the reduction process. In agreement with bulk electrolysis findings, the CV analysis supported by simulation indicated that hydrogen evolution is still the dominant electrode reaction in pyridine-containing electrolyte solution, even with an excess CO2 concentration in the solution. No prominent contribution from either a direct or coupled CO2 reduction was found. The results obtained suggest that the reduction of CO2 to methanol is a transient process that is largely decoupled from the electrode charge transfer.