A chiral surprise in the rainforest

August 27, 2020

Forests such as the Amazon rainforest emit huge amounts of biogenic volatile organic compounds (BVOC) into the atmosphere. These compounds impact the physical and chemical properties of the atmosphere and also our climate. The molecules react rapidly with ambient OH radicals and ozone, thereby influencing the oxidation capacity of the atmosphere for pollutants such as carbon monoxide and greenhouse gases such as methane. Furthermore, BVOC are precursors to secondary organic aerosols, which affect the Earth's radiative budget.

Many BVOCs such as ?-pinene are chiral. This means that they exist in two non-superimposable mirror image forms just like our left and right hands. Scientists speak of enantiomers, or plus and minus forms. However, all physical properties such as their boiling point, mass and their reaction rate with atmospheric oxidizing agents like OH and ozone are identical.

Despite the chemical similarity of these chiral pairs, insects and plants can distinguish enantiomeric forms of pheromones and phytochemicals, although little attention has been paid to the mixing ratio of the two separated forms in forests. Previous measurements reported minus α-pinene to be the dominant chiral molecule of the tropical forest. Scientists from the Max Planck Institute for Chemistry, the Johannes Gutenberg-University Mainz and from Brazil have now made a surprising discovery: from the 325-meter-high measuring tower in the Amazon rainforest, they were able to show that the ratio of the α-pinene enantiomers varies in the vertical by a factor of ten. The team around the Max Planck researcher Nora Zannoni was also able to demonstrate that the concentrations are altitude-dependent and vary with the time of day and in both wet and dry seasons.

While plus-α-pinene dominates at 40 meters anytime and at 80 meters during the night, the minus form predominates at 80 meters during the day and at all other higher heights anytime. The team also observed that the minus α-pinene concentration depends on temperature at 80 meters while plus α-pinene does not. "The photosynthetic activity of the vegetation depends on temperature and stomatal opening. It thus drives the emissions of minus α-pinene, demonstrating that leaves are the main source of emission of this isomer, and that the two isomers are released from leaves through different pathways", says Zannoni, who is first author of a study recently published in the science magazine "Communications Earth & Environment".

Termites as unknown source of plus α-pinene in the canopy?

During the dry season, the chiral ratio of the two forms reverses at 80 meters. "This indicates a strong, uncharacterized source of plus α-pinene in the canopy," says Jonathan Williams, group leader at the institute in Mainz and last author of the study. Since the researchers could rule out atmospheric sinks such as the chiral-selective degradation of pinene by OH radicals and ozone or deposition onto aerosols as well as the influence of wind direction and sunlight, they instead suspect that insect stresses such as herbivores feeding and termites emissions are responsible for the plus α-pinene higher values. In order to test a possible impact of insects the researchers conducted additional measurements above termite nests which confirmed that such emissions can overturn the ambient chiral ratio of α-pinene. As termite populations are expected to increase significantly in the future with continued deforestation and climate warming, their influence needs to be considered in forest emission models and forest signaling.

"We also know that plants can release large amounts of plus α-pinene when injured or eaten," Williams adds. This is supported by measurements of volatile compounds associated with leaf wounding that even revealed when the herbivores were most active. The atmospheric chemists Zannoni and Williams conclude that they need to rethink how canopy emissions of volatile organic compounds are simulated, and take the whole ecosystem into account.
The research was co-financed by the H2020 project "ULTRACHIRAL" of the European Union.

Max Planck Institute for Chemistry

Related Ozone Articles from Brightsurf:

Investigating the causes of the ozone levels in the Valderejo Nature Reserve
The UPV/EHU's Atmospheric Research Group (GIA) has presented a database comprising over 60 volatile organic compounds (VOC) measured continuously over the last ten years in the Valderejo Nature Reserve (Álava, Basque Country).

FSU Research: Despite less ozone pollution, not all plants benefit
Policies and new technologies have reduced emissions of precursor gases that lead to ozone air pollution, but despite those improvements, the amount of ozone that plants are taking in has not followed the same trend, according to Florida State University researchers.

Iodine may slow ozone layer recovery
Air pollution and iodine from the ocean contribute to damage of Earth's ozone layer.

Ozone threat from climate change
We know the recent extreme heat is something that we can expect more of as a result of increasing temperatures due to climate change.

Super volcanic eruptions interrupt ozone recovery
Strong volcanic eruptions, especially when a super volcano erupts, will have a strong impact on ozone, and might interrupt the ozone recovery processes.

How severe drought influences ozone pollution
From 2011 to 2015, California experienced its worst drought on record, with a parching combination of high temperatures and low precipitation.

New threat to ozone recovery
A new MIT study, published in Nature Geoscience, identifies another threat to the ozone layer's recovery: chloroform -- a colorless, sweet-smelling compound that is primarily used in the manufacturing of products such as Teflon and various refrigerants.

Ozone hole modest despite optimum conditions for ozone depletion
The ozone hole that forms in the upper atmosphere over Antarctica each September was slightly above average size in 2018, NOAA and NASA scientists reported today.

Increased UV from ozone depletion sterilizes trees
UC Berkeley paleobotanists put dwarf, bonsai pine trees in growth chambers and subjected them to up to 13 times the UV-B radiation Earth experiences today, simulating conditions that likely existed 252 million years ago during the planet's worst mass extinction.

Ozone at lower latitudes is not recovering, despite Antarctic ozone hole healing
The ozone layer -- which protects us from harmful ultraviolet radiation -- is recovering at the poles, but unexpected decreases in part of the atmosphere may be preventing recovery at lower latitudes.

Read More: Ozone News and Ozone Current Events
Brightsurf.com is a participant in the Amazon Services LLC Associates Program, an affiliate advertising program designed to provide a means for sites to earn advertising fees by advertising and linking to Amazon.com.