image: An image of Venus captured in 1974 by the Mariner 10 mission was recently reprocessed, enabling more detail to become visible. Areas of reddish clouds, about 40 miles above the planet’s surface, indicate ultraviolet absorption, the source of which is a long, unsolved scientific mystery. New work by researchers from Penn and other institutions help clarify the sulfur chemistry at play in the clouds, which may be involved in absorbing UV light. The findings have implications for chemistry on Earth. view more
Credit: NASA/JPL-Caltech
High in the atmosphere of Venus, a swirl of sulfur-containing clouds blankets the planet. Dark spots in these clouds correspond with areas of high ultraviolet light absorption, but researchers have yet to confirm the chemical culprit responsible for this activity.
In a recent study, scientists using sophisticated computational chemistry techniques have identified a new pathway for how sulfur particles can form in the Venusian atmosphere. The results clarify the planet’s source of sulfur-rich clouds, hint at the identity of the long-mysterious ultraviolet-absorbing compound, and offer a note of caution for efforts to geoengineer a solution to climate change by injecting sulfur into Earth’s atmosphere.
“Scientists have been trying to understand the source of these ultraviolet absorbing emissions on Venus for a while,” says Joseph S. Francisco, an atmospheric chemist at the University of Pennsylvania and a corresponding author on the new work, published in Nature Communications. “To date, none of these emissions correspond to anything that we know here on Earth. That’s sparked a lot of interest and excitement because that means there is some new chemistry to discover.”
“We know that the atmosphere of Venus has abundant SO2 (sulphur dioxide) and sulfuric acid particles,” says James Lyons, senior scientist at the Planetary Science Institute and another corresponding author on the paper. “We expect that ultraviolet destruction of SO2 produces sulfur particles. They are built up from atomic S (sulfur) to S2 (disulfur), then S4 and finally S8. But how is this process initiated, that is, how does S2 form?”
Earlier efforts had hypothesized one possibility: that S2 formed from two sulfur atoms, that is, reaction of S and S. Molecules of S2 and S2 can then combine to form S4, and so on. Sulfur particles can form either by condensation of S8 or by condensation of S2, S4 and other allotropes—different physical forms in which an element can exist—which then rearrange to form condensed S8.
Francisco and Penn postdoc Tarek Trabelsi, however, looked to identify a different pathway to form S2 that could more accurately model what was known about sulfur chemistry in Venus’ atmosphere. Laboratory experiments involving sulfur, chlorine, and oxygen can be difficult and even hazardous, making computational methods an appealing alternative. Working with colleagues from Spain, they developed state-of-the-art computational models that factored in the wave lengths of light that would cause sulfur to compounds to break apart and the rates at which they would do so. Lyons and other colleagues incorporated those calculations into atmospheric models of Venus.
Together, their work revealed a new and faster pathway to form S2, involving a reaction between sulfur monoxide (SO) and disulfur monoxide (S2O), with interactions with chlorine compounds as an intermediate step.
“This research illustrates another pathway to S2 and sulfur particle formation,” Lyons says. “Sulfur chemistry is dominant in Venus' atmosphere and very likely plays a key role in the formation of the enigmatic UV (ultraviolet) absorber. More generally, this work opens the doors to using molecular techniques to disentangle the complex chemistry of Venus.”
Francisco adds that the findings can also help in weighing what to avoid when it comes to chemistry on Earth. While some scientists and engineers have proposed adding sulfur compounds like sulfur dioxide and trioxide into the Earth’s atmosphere to reflect light and reduce the impacts of climate change, Francisco notes that many unknowns exist about how such an intervention would play out.
“Knowing what chemistry takes place on other planets helps guide us in understanding new chemistry that might occur on Earth and what we don’t want to happen in Earth’s atmosphere,” he says.
Joseph S. Francisco is President’s Distinguished Professor in the Department of Earth and Environmental Science and Department of Chemistry in the University of Pennsylvania School of Arts & Sciences.
Francisco and Lyons’ coauthors on the work were Penn’s Tarek Trabelsi; Antonio Francés-Monerris, Javier Carmona-García, and Daniel Roca-Sanjuán of the Universitat de València, Spain; and Alfonso Saiz-Lopez of the Institute of Physical Chemistry Rocasolano in Madrid. Francés-Monerris was lead author and Francisco, Francés-Monerris, Lyons, and Roca-Sanjuán were co-corresponding authors.
The study was supported in part by Generalitat Valenciana and the European Social Fund, the Ministerio de Ciencia e Innovación, and “la Caixa” Foundation.
Adapted from a press release by Alan Fischer, Planetary Science Institute, fischer@psi.edu or 520-382-041
Journal
Nature Communications
Method of Research
Computational simulation/modeling
Subject of Research
Not applicable
Article Title
Photochemical and thermochemical pathways to S2 and polysulfur formation in the atmosphere of Venus
Article Publication Date
30-Jul-2022