Cooperative Institute for Research in Environmental Sciences

Atmospheric Breakdown

Atmospheric Breakdown

New study finds some chemicals less damaging to the ozone layer can degrade to form long-lived greenhouse gases

Some substitutes for ozone-damaging chemicals being phased out worldwide under international agreements are themselves potent greenhouse gases and contribute to warming. Now, a new study in Geophysical Research Letters shows for the first time how some of those replacement chemicals can break down in the atmosphere to form a greenhouse gas that can persist for millennia, much longer than the substitute chemicals themselves.

Specifically, when some chemicals widely used as refrigerants break down in the stratosphere—a layer in the middle atmosphere—under some conditions, they can form a potent greenhouse gas that lasts for up to 50,000 years, according to scientists from the Cooperative Institute for Research in Environmental Sciences (CIRES) at the University of Colorado Boulder and the NOAA Earth System Research Laboratory (ESRL) in Boulder.

Lab equipment. A new study shows for the first time how some chemicals can break down in the atmosphere, forming a greenhouse gas that can persist for millennia. Aaron Jubb works on a laboratory setup used to measure the reactivity and photochemistry of atmospherically relevant species. Photo: Will von Dauster/ NOAA

“This compound, carbon tetrafluoride or CF4, essentially lasts forever because there aren’t any known removal mechanisms in the atmosphere,” said James Burkholder, a research chemist at NOAA ESRL and coauthor of the study.

Lead author Aaron Jubb, a CIRES scientist working at NOAA ESRL and now at Oak Ridge National Laboratory, did the laboratory work showing how CF4 can be made from some halocarbons, chemicals that include HFCs and HCFCs and are substitutes for the more ozone-damaging chemicals that have largely been phased out. Jubb started with trifluoroacetyl fluoride—a compound produced in the atmosphere when some halocarbons breaks down—exposed it to short-wavelength UV radiation, and looked at the reaction products that formed. CF4 was one of those breakdown products.

The amount of CF4 produced by this photochemical process was shown to be a small fraction of atmospheric CF4; industrial sources are much larger emitters of CF4. Still, identifying this particular source of such a potent and lasting greenhouse gas is important, particularly since its production could continue to grow depending on which “parent” products are used by industry.

“We really need to understand the chemistry of the compounds we use,” said Jubb. “Even as we move towards shorter-lived halocarbons for industrial use, during atmospheric degradation they can produce a long-lived atmospheric effect.”

This work was supported in part by NOAA’s Atmospheric Chemistry, Carbon Cycle, and Climate (AC4) Program and NASA’s Atmospheric Composition Program. 

CIRES is a partnership of NOAA and CU Boulder.

Authors of  “An atmospheric photochemical source of the persistent greenhouse gas CF4” are Aaron Jubb (Cooperative Institute for Research in Environmental Sciences and NOAA Earth System Research Laboratory, ESRL; Chemical Sciences Division, now at Oak Ridge National Laboratory), Max McGillen (Cooperative Institute for Research in Environmental Sciences and NOAA ESRL Chemical Sciences Division), Robert W. Portmann (NOAA ESRL Chemical Sciences Division),  John S. Daniel (NOAA ESRL Chemical Sciences Division), and James B. Burkholder (NOAA ESRL Chemical Sciences Division).  
NOAA ESRL CSD, Chemical Processes & Instrument Development Group                  


James Burkholder
NOAA scientist
Aaron Jubb
(former) CIRES scientist
Karin Vergoth
CIRES communications
(303) 497-5125


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