Rain as acidic as undiluted lemon juice may have played a part in killing off plants and organisms around the world about 252 million years ago during the most severe mass extinction in Earth's history, known as the Great Dying.

The cause of such a massive extinction is an ongoing scientific debate, centering on several potential causes, including an asteroid collision similar to what likely killed off the dinosaurs 186 million years later; a gradual, global loss of oxygen in the oceans; and a cascade of environmental events triggered by massive volcanic eruptions in a region known today as the Siberian Traps.

Scientists writing in
Geology
simulated this last possibility, creating global climate models of scenarios in which repeated bursts of volcanism spew gases, including sulfur, into the atmosphere. From their simulations, they found that sulfur emissions were significant enough to create widespread acid rain throughout the Northern Hemisphere, with pH levels reaching 2 — as acidic as undiluted lemon juice. They say such acidity may have been sufficient to disfigure plants and stunt their growth, contributing to their ultimate extinction.

"Imagine you're a plant that's growing happily in the latest Permian," says Dr. Benjamin Black, a post-doctoral researcher in MIT's Department of Earth, Atmospheric and Planetary Sciences, lead author of the paper. "It's been getting hotter and hotter, but perhaps your species has had time to adjust to that. But then quite suddenly, over the course of a few months, the rain begins to sizzle with sulfuric acid. It would be quite a shock if you were that plant."

Lemon juice spike

Geologists who have examined the rock record in Siberia have observed evidence of immense volcanism that came in short bursts beginning near the end of the Permian period and continuing for another million years. The volume of magma totaled several million cubic kilometers — enough to completely blanket the continental United States. This boiling stew of magma likely released carbon dioxide and other gases into the atmosphere, leading to gradual but powerful global warming.

The eruptions may also have released large clouds of sulfur, which ultimately returned to Earth's surface as acid rain. Black, who has spent several summers in Siberia collecting samples to measure sulfur and other chemicals preserved in igneous rocks, used these measurements, along with other evidence, to develop simulations of magmatic activity in the end-Permian world.

The group simulated 27 scenarios, each approximating the release of gases from a plausible volcanic episode, including medium eruptions, large eruptions, and magma erupted through explosive pipes in the Earth's crust. The researchers included a wide range of gases in their simulations, based on estimates from chemical analyses and thermal modeling. They then tracked water in the atmosphere, and the interactions among various gases and aerosols, to calculate the pH of rain.

The results showed that both carbon dioxide and volcanic sulfur could have significantly affected the acidity of rain at the end of the Permian. Levels of carbon dioxide and other greenhouse gases may have risen rapidly at the time, in part because of Siberian volcanism. According to their simulations, the researchers found that this elevated carbon dioxide could have increased rain's acidity by an order of magnitude.

Adding sulfur emissions to the mix, they found that acidity further spiked to a pH of 2 — as acidic as undiluted lemon juice — and that such acidic rain may have fallen over most of the Northern Hemisphere. After an eruption ended, the researchers found that pH levels in rain bounced back, becoming less acidic within one year. However, with repeated bursts of volcanic activity, Black says the resulting swings in acid rain could have greatly stressed terrestrial species.

"Plants and animals wouldn't have much time to adapt to these changes in the pH of rain," Black says. "I think it certainly contributed to the environmental stress which was making it difficult for plants and animals to survive. At a certain point you have to ask, 'How much can a plant take?'"

Life as an end-Permian organism

In addition to acid rain, the researchers modeled ozone depletion resulting from volcanic activity. While ozone depletion is more difficult to model than acid rain, their results suggest that a mix of gases released into the atmosphere may have destroyed 5 to 65 percent of the ozone layer, substantially increasing species' exposure to ultraviolet radiation. The greatest ozone depletion occurred near the poles.

Going forward, Black hopes paleontologists and geochemists will consider the results as a point of comparison for their own observations of the end-Permian mass extinction. In the meantime, he says he now has a much more vivid picture of that catastrophic time.

"It's not just one thing that was unpleasant," Black says. "It's this whole host of really nasty atmospheric and environmental effects. These results really made me feel sorry for end-Permian organisms."