A novel free-air diesel and ozone enrichment (FADOE) research platform.

Air pollution is an escalating concern in the modern world, posing substantial threats to ecosystem processes. While the importance of comprehending the impact of pollutants on natural environments is evident, conducting rigorous field-based experiments presents formidable challenges. Elevating pollutant concentrations within open air environments in a controlled manner is complex. Nonetheless, such real-world experiments are invaluable for revealing the genuine influence of air pollutants on ecosystems and their functioning. Field-scale measurements have emerged as a pivotal avenue for advancing our understanding of the interactions between air pollutants and the natural world, providing unique insights into ecosystem dynamics, including critical processes like pollination and natural pest regulation. In atmospheric and ecological research, free-air exposure systems have proven effective in elevating carbon dioxide (CO2) and ozone (O3) concentrations, facilitating the exploration of their ecological consequences. Yet, nitrogen oxides (NOx), a class of pollutants with significant ecological and atmospheric relevance, have largely eluded field-based ecological investigations. This paper introduces the recently developed FADOE (Free-Air Diesel and Ozone Enrichment) platform, which allows the elevation of O3 and diesel exhaust (including NOx) within a field-scale context. Comprehensive information on the system's design, construction, and performance data from the 2023 summer season is presented.•Air pollution and ecosystem functioning•Elevated ozone and nitrogen oxides (NOx)•Free-air exposure systems for field scale measurements.

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.

Deposition of α-pinene oxidation products on plant surfaces affects plant VOC emission and herbivore feeding and oviposition.

White cabbage, Brassica oleracea, plants and artificial leaves covered with B. oleracea epicuticular wax were exposed to α-pinene and α-pinene oxidation products formed through the oxidation of α-pinene by ozone (O3) and hydroxyl (OH) radicals. O3 and OH-induced oxidation of α-pinene led to the formation of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol particles (SOA), referred to together as oxidation products (OP). Exposure of cabbage plants to O3 and OH-induced α-pinene OP led to the deposition and re-emission of gas-phase OP by exposed cabbage plants. In a series of 2-choice bioassays, the specialist cruciferous herbivore, Plutella xylostella adults deposited less eggs on artificial leaves exposed to α-pinene OP than on control plants exposed to clean filtered air. P. xylostella larvae did not show a specific feeding preference when offered leaves from different exposure treatments. However, the generalist Indian stick insect, Carausius morosus, fed more on control filtered air-exposed plants than on those exposed to α-pinene OP. Taken together, our results show that exposure to α-pinene oxidation products affects VOC emissions of B. oleracea and alters P. xylostella oviposition and C. morosus feeding responses.

Understorey Rhododendron tomentosum and Leaf Trichome Density Affect Mountain Birch VOC Emissions in the Subarctic.

Subarctic vegetation is composed of mountain birch [Betula pubescens ssp. czerepanovii (MB)] forests with shrubs and other species growing in the understorey. The effects of the presence and density of one understorey shrub, Rhododendron tomentosum (RT), on the volatile emissions of MB, were investigated in a Finnish subarctic forest site in early and late growing season. Only MB trees with an RT-understorey emitted the RT-specific sesquiterpenoids, palustrol, ledol and aromadendrene. Myrcene, which is the most abundant RT-monoterpene was also emitted in higher quantities by MB trees with an RT-understorey. The effect of RT understorey density on the recovery of RT compounds from MB branches was evident only during the late season when sampling temperature, as well as RT emissions, were higher. MB sesquiterpene and total emission rates decreased from early season to late season, while monoterpene emission rate increased. Both RT and MB terpenoid emission rates were linked to density of foliar glandular trichomes, which deteriorated over the season on MB leaves and emerged with new leaves in the late season in RT. We show that sesquiterpene and monoterpene compounds emitted by understorey vegetation are adsorbed and re-released by MB, strongly affecting the MB volatile emission profile.

Ozone disrupts adsorption of Rhododendron tomentosum volatiles to neighbouring plant surfaces, but does not disturb herbivore repellency.

The perennial evergreen woody shrub, Rhododendron tomentosum, confers associational resistance against herbivory and oviposition on neighbouring plants through passive adsorption of some of its constitutively emitted volatile organic compounds (VOCs). The adsorption process is dependent on transport of VOCs in the air. In polluted atmospheres, the VOCs may be degraded and adsorption impeded. We studied the effect of elevated ozone regimes on the adsorption of R. tomentosum volatiles to white cabbage, Brassica oleracea, and the oviposition of the specialist herbivore Plutella xylostella on the exposed plants. We found evidence for adsorption and re-emission of R. tomentosum volatiles by B. oleracea plants. Ozone changed the blend of R. tomentosum volatiles and reduced the amount of R. tomentosum volatiles recovered from B. oleracea plants. However, plants exposed to R. tomentosum volatiles received fewer P. xylostella eggs than control plants exposed to filtered air irrespective of whether R. tomentosum volatiles mixed with ozone. Ozone disrupts a volatile mediated passive plant-to-plant interaction by degrading some compounds and reducing the quantity available for adsorption by neighbouring plants. The change, however, did not affect the deterrence of oviposition by P. xylostella, suggesting that aromatic companion plants of Brassica crops may confer pest-deterring properties even in ozone-polluted environments.

Passive Adsorption of Volatile Monoterpene in Pest Control: Aided by Proximity and Disrupted by Ozone.

Plant volatiles mediate a range of interactions across and within trophic levels, including plant-plant interactions. Volatiles emitted by a plant may trigger physiological responses in neighboring plants or adhere to their surfaces, which, in turn, may affect the responses of the neighboring plant to herbivory. These volatiles are subject to chemical reactions during transport in air currents, especially in a polluted atmosphere. We conducted a field experiment to test for the adsorption of dispenser-released myrcene on the surfaces of cabbage plants and the effects of distance from the dispenser and elevated ozone levels (1.4× ambient) on the process. We also tested the effects of the same treatments on oviposition on cabbage plants by naturally occurring Plutella xylostella. Under low ambient ozone conditions of central Finland, there was evidence for the adsorption and re-release of myrcene by cabbage plants growing at a distance of 50 cm from myrcene dispensers. This effect was absent at elevated ozone levels. The number of eggs deposited by P. xylostella was generally lower in plots under elevated ozone compared to ambient control plots. Our results indicate that passive adsorption and re-release of a volatile monoterpene can occur in nature; however, this process is dependent upon the distance between emitter source and receiver plants as well as the concentration of atmospheric pollutants in the air. We conclude that, in the development of field-scale use of plant volatiles in modern pest control, the effects of distances and air pollution should be considered.