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Stronger Culprits Found for Global Warming

November 17, 2009

A new study indicates that major chemicals most often cited as leading causes of climate change, such as carbon dioxide and methane, are outclassed in their warming potential by compounds receiving less attention.


Purdue Univ. and NASA examined more than a dozen chemicals, most of which are generated by humans, and have developed a blueprint for the underlying molecular machinery of global warming. The results appear in the American Chemical Society's Journal of Physical Chemistry A.

The compounds, which contain fluorine atoms, are far more efficient at blocking radiation in the "atmospheric window," says Purdue Professor Joseph Francisco, who helped author the study. The atmospheric window is the frequency in the infrared region through which radiation from Earth is released into space, helping to cool the planet. When that radiation is trapped instead of being released, a "greenhouse effect" results, warming the globe. Most of the chemicals in question are used industrially, he says.

NASA scientist Timothy Lee, lead author of the study with Francisco and NASA postdoctoral fellow Partha Bera, characterized the fluorinated compounds as having the potential to quickly slam the atmospheric window shut, as opposed to gradually easing it shut like carbon dioxide.

In the results, chemicals such as chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur and nitrogen fluorides stood out in their warming potential because of their efficiency to trap radiation in the atmospheric window.

"It's actually rather stark," says Francisco, a Purdue chemistry and earth and atmospheric sciences professor, whose research focuses on the chemistry of molecules in the atmosphere.

An understanding of how the chemicals contribute to climate change on a molecular scale affords the opportunity to create benign alternatives and to test new chemicals for their global warming capability before they go to market, Francisco says. "Now you have a rational design basis."

The researchers looked at more than a dozen chemicals, often referred to as "greenhouse gases," listed as warming agents by the Intergovernmental Panel on Climate Change, the most prominent international scientific group monitoring global warming. The study employed both results from experimental observations and from computer modeling using supercomputers from Information Technology at Purdue (ITaP), Purdue's central information technology organization, and NASA. The goal was to determine which chemical and physical properties are most important in contributing to global warming.

"Believe it or not, nobody has ever delineated these properties," Lee says.

CFC use has waned with the discovery that the chemicals contribute to the destruction of Earth's ozone layer, which absorbs most of the dangerous ultraviolet radiation from the sun. But HFCs and PFCs are widely used in air conditioning and the manufacturing of electronics, appliances and carpets. Other uses range from application as a blood substitute in transfusions to tracking leaks in natural gas lines.

"Although current concentrations of some of these trace gases have been found to be substantially small compared to carbon dioxide, their concentration is on the rise," the study notes. "With the current rate of increase, they will be important contributors in the future, according to some models."

The fluorine atoms that characterize the chemicals are highly electro-negative and tend to pull electrons to themselves, Francisco says. This shift makes the molecules more efficient at absorbing radiation, which would normally bleed harmlessly into space. As a result, the fluorine-containing compounds are the most effective global warming agents, the study concludes.

The compounds also persist longer than carbon dioxide and other major global warming agents, says Lee, chief of the Space Science and Astrobiology Division at NASA Ames Research Center. The concern is that, even if emitted into the atmosphere in lower quantities, the chemicals might have a powerful cumulative effect over time. Some of these chemicals don't break down for thousands of years.

Source: Purdue Univ.


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Comments
Tom 10/1/2010 11:50:28 AM
Are these computer generated greenhouse results from the same type of programing used for CO2. Since we now know CO2 forms in higher concentrations in the environment AFTER the environment warms, to help in the cooling by generating food for algae and plant life. have these Federally funded researchers checked for what beneficial results may be obtained from changes in the flouride based compounds in the environment? The ozone scare was also based on false science. Maybe we don't want to be considered in the same low class as Mr. Gore and others who scream the sky is falling for profit.

Wally 6/14/2010 1:02:32 PM
While it may be true that flourocarbon gases are effective "greenhouse gases", their concentration compared to water vapor and other important "greenhouse gases" is infinitesimal. Also, the theory that they caused the "ozone hole" is nonsense. The molecular weight of R-12, the most maligned of the refrigerants is about 121 compared to the molecular weight of N2 of only 28 and O2 at 32. Even Co2 with a molecular weight of 44 starts "dropping out" at altitudes far below the "ozone layer. The "ozone hole" is a direct result of turbulance at the poles, especially the South Pole caused by material from solar flares entering the atmosphere at the poles and the fact that convection causes the atmosphere to rise at mid latitudes and sink at the poles thus dispersing the high altitude ozone at the poles. Just another scam!

Leonard Weinstein 3/15/2010 12:26:50 PM
Robby B, It does not matter if there is a physical barrier or greenhouse gas present, the temperature increases until a new balance level is reached (unless something is still changing, such as continual increases of greenhouse gasses). Once that new level is reached, the outgoing radiation has to be equal to incoming. It is true this will be at a higher ground temperature, but once the level of greenhouse gas is not changing more, the energy will be balanced. The inbalance is a feature of continuing change on the greenhouse level, not the fact that there is a greenhouse effect.

Steve H 3/14/2010 7:12:37 PM
Makes me wonder why the EPA has delisted chemicals such as PCBTF as being VOC's!!

Myles Phipps 1/29/2010 4:13:19 PM
The atmosphere isn't smart enough to tell. Instead, the important thing not yet mentioned is that the atmosphere is essentially transparent to visible light (which is, actually, why it's "visible"...our eyes evolved to be able to sense this abundant source). The atmosphere is not nearly so transparent to infrared,which is of longer wavelength than visible. It's a general property of the process of absorbtion and re-radiation of light that the re-emittee light is of a longer wavelength that which was absorbed. This is a result of, among other things, conservation of momentum and of energy. So the re-radiated light will be of longer wavelength than the relatively shorter visible light that came in. So the atmosphere doesn't need to be smart to tell the difference. The energy and momentum of the incoming light allows ready passage through the atmosphere. The longer wavelength re-emitted light isn't able to pass out. Two important points: Note that when the longer wavelength light is blocked, most of the energy goes into changing the energy state of the molecules that did the absorbing, i.e by changing their vibrational and rotational states, in short they themselves become hotter. Also that the difference between the energy brought to the surface as visible light and the energy released when it's re-radiated is not lost. It heats up the materials of the ground, and their temperature must rise in consequence. So unless there's some other way for the energy to escape, we're warming both the ground materials and the atmosphere. Rapid global temperatures should result, perhaps even more rapidly than would seem likely at first glance.

TimR 1/29/2010 2:04:03 PM
Sounds like we need to keep most if not all, fluorine-containing compounds out of the atmosphere. Too bad ...fluoro-compounds are so darn useful....

Russ H 1/24/2010 11:45:50 PM
Mark, you are on the right track! I'm with Bill Roberts on this one.

Bill Roberts 12/16/2009 11:54:42 AM
Mark Cheek's comment and Robby B's answer raised this question in my mind: Would a hypothetical "greenhouse" that had no glass, but rather a membrane that was transparent to all wavelengths, including IR, become warmer than the ambient temperature outside the greenhouse. In other words, is the effect due more to the restriction of convection than to the trapping of radiation? A rather large portion of the sun's radiation is in the IR range and blocking that with glass would certainly reduce the heating effect of solar radiation.

Robby B 11/25/2009 10:39:17 PM
Mark, good question. But this one has an answer. In the most basic terms, the greenhouse effect occurs when more radiation passes inbound through the enclosure (e.g. glass for a greenhouse or the atmosphere for the Earth) than outbound through the enclosure. For simplicity, consider a greenhouse that is 100% transparent to visible light, but reflects 100% of infrared light. For argument's sake, assume that no other E-M radiation falls on the greenhouse or is produced inside. This is an over-simplification, which can be accounted for in subsequent, more refined analysis of the situation. Also, ignore other energy sources within the greenhouse for now. So, visible light flows into the greenhouse. Some of the visible light is reflected from the greenhouse contents -- and passes back out of the greenhouse. The rest is absorbed -- much of it as heat. Warm objects radiate infrared light. The infrared radiated from inside the greenhouse is reflected back in -- and partially reabsorbed (and re-radiated as heat). That is what makes the greenhouse "smart" enough to distinguish inbound from outbound radiation. To a large extent, the same is true of the Earth and its atmosphere. In fact, analyzing one-by-one the details that were set aside for argument's sake above, you find that many (although not all) of those interactions exacerbate the overheating effects. Still, it is a good question. Mark deserves, for clarity, the simplified answer given above. But, as Mark's query suggests, there is more to it. So, the question deserves careful attention to the real effects of everything that that simplified answer ignored. Some is available now. Some, like what was reported in the above article, had been overlooked. And some may not have even been imagined yet. This kind of questioning and thinking leads to useful developments in the current struggle to assure a viable future for human beings on our planet Earth. Robby B.

Mark Cheek 11/17/2009 12:37:03 PM
I am wondering if these chemicals are "smart" enough to recognize radiation that is earth based versus radiation from our solar system. Seems that this window would keep out, as well as keep in radiation.

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Michelle Longo
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