Who would have guessed it? Sunlit snow key to Arctic ozone depletion

I like this study from the NSF, because they did hands-on empirical measurements and experiments to make  the determination – Anthony

Sunlit Snow Triggers Atmospheric Cleaning, Ozone Depletion in the Arctic

Finding is related to snow atop sea ice, adding a new dimension to scientific concerns about loss of Arctic ice

Scientist conductiong a snow-chamber experiment

Kerri Pratt conducts a snow-chamber experiment near Barrow, Alaska.

Credit and Larger Version

April 19, 2013

National Science Foundation-funded researchers at Purdue University have discovered that sunlit snow is the major source of atmospheric bromine in the Arctic, the key to unique chemical reactions that purge pollutants and destroy ozone.

The new research also indicates that the surface snowpack above Arctic sea ice plays a previously unappreciated role in the bromine cycle and that loss of sea ice, which been occurring at an increasingly rapid pace in recent years, could have extremely disruptive effects in the balance of atmospheric chemistry in high latitudes.

The team’s findings suggest the rapidly changing Arctic climate–where surface temperatures are rising three times faster than the global average–could dramatically change its atmospheric chemistry, said Paul Shepson, an NSF-funded researcher who led the research team. The experiments were conducted by Kerri Pratt, a postdoctoral researcher funded by the Division of Polar Programs in NSF’s Geosciences Directorate.

“We are racing to understand exactly what happens in the Arctic and how it affects the planet because it is a delicate balance when it comes to an atmosphere that is hospitable to human life,” said Shepson, who also is a founding member of the Purdue Climate Change Research Center. “The composition of the atmosphere determines air temperatures, weather patterns and is responsible for chemical reactions that clean the air of pollutants.”

A paper detailing the results of the research, some of which was funded by NSF and some by the National Aeronautics and Space Administration, was recently published online at Nature Geoscience.

Ozone in the lower atmosphere behaves differently from the stratospheric ozone involved in the planet’s protective ozone layer. This lower atmosphere ozone is a greenhouse gas that is toxic to humans and plants, but it also is an essential cleaning agent of the atmosphere.

Interactions between sunlight, ozone and water vapor create an “oxidizing agent” that scrubs the atmosphere of most of the pollutants human activity releases into it, Shepson said.

Temperatures at the poles are too cold for the existence of much water vapor and in the Arctic this cleaning process appears instead to rely on reactions on frozen surfaces involving molecular bromine, a halogen gas derived from sea salt.

This gaseous bromine reacts with and destroys atmospheric ozone. This aspect of the bromine chemistry works so efficiently in the Arctic that ozone is often entirely depleted from the atmosphere above sea ice in the spring, Shepson noted.

“This is just a part of atmospheric ozone chemistry that we don’t understand very well, and this unique Arctic chemistry teaches us about the potential role of bromine in other parts of the planet,” he said. “Bromine chemistry mediates the amount of ozone, but it is dependent on snow and sea ice, which means climate change may have important feedbacks with ozone chemistry.”

While it was known that there is more atmospheric bromine in polar regions, the specific source of the natural gaseous bromine has remained in question for several decades, said Pratt, a Polar Programs-funded postdoctoral fellow and lead author of the paper.

“We thought that the fastest and best way to understand what is happening in the Arctic was to go there and do the experiments right where the chemistry is happening,” Pratt said.

She and Purdue graduate student Kyle Custard performed the experiments in -45 to -34 Celsius (-50 to -30 Fahrenheit) wind chills near Barrow, Alaska. The team examined first-year sea ice, salty icicles and snow and found that the source of the bromine gas was the top surface snow above both sea ice and tundra.

“Sea ice had been thought to be the source of the gaseous bromine,” she said. “We had an ‘of course!’ moment when we realized it was the snow on top of the sea ice. The snow is what is in direct contact with the atmosphere. Sea ice is critical to the process, though. Without it, the snow would fall into the ocean, and this chemistry wouldn’t take place. This is among the reasons why the loss of sea ice in the Arctic will directly impact atmospheric chemistry.”

The team also discovered that sunlight triggered the release of bromine gas from the snow and the presence of ozone increased the production of bromine gas.

“Salts from the ocean and acids from a layer of smog called Arctic haze meet on the frozen surface of the snow, and this unique chemistry occurs,” Pratt said. “It is the interface of the snow and atmosphere that is the key.”

A series of chemical reactions that quickly multiplies the amount of bromine gas present, called the “bromine explosion,” is known to occur in the atmosphere. The team suggests this also occurs in the spaces between the snow crystals and wind then releases the bromine gas up into the air above the snow.

The team performed 10 experiments with snow and ice samples contained in a “snow chamber,” a box constructed of aluminum with a special coating to prevent surface reactions and a clear acrylic top. Clean air with and without ozone was allowed to flow through the chamber and experiments were performed in darkness and in natural sunlight.

The team also measured the levels of bromine monoxide, a compound formed from the reaction of bromine atoms with ozone, through flights of the Purdue Airborne Laboratory for Atmospheric Research.

Shepson is the pilot of this specially equipped aircraft, which he and air operations technical specialist Brian Stirm flew from Indiana to Barrow for these experiments. They found the compound was most prevalent over snow-covered first-year sea ice and tundra, consistent with their snow chamber experiments.

The experiments were performed from March to April 2012 and were part of NASA’s Bromine, Ozone and Mercury Experiment, or BROMEX. The goal of the study is to understand the implications of Arctic sea ice reduction on tropospheric chemistry.

Shepson’s group next plans to perform laboratory studies to test the proposed reaction mechanisms and to return to Barrow to perform more snow chamber experiments.

In addition, Shepson is co-leading a team using ice-tethered buoys to measure carbon dioxide, ozone and bromine monoxide across the Arctic Ocean, and Pratt is working with scientists from the University of Washington to examine the chemistry of snow from across the Arctic Ocean.

“In the Arctic, climate change is happening at an accelerated pace,” Pratt said. “A big question is what will happen to atmospheric composition in the Arctic as the temperatures rise and snow and ice decline even further?”

-NSF-

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AndyG55
April 25, 2013 3:28 am

“In the Arctic, climate change is happening at an accelerated pace,”
Gees, if you look at this years temps, they are pretty darn close to the ERA 40 year average, and WAY below any melting !!
http://ocean.dmi.dk/arctic/plots/meanTarchive/meanT_2013.png

April 25, 2013 3:47 am

Ozone in the lower atmosphere behaves differently from the stratospheric ozone involved in the planet’s protective ozone layer.

So let me get this straight – this is nothing to do with the “Ozone Hole” we hear so much about (especially here in New Zealand) caused supposedly by CFC’s etc – but is all to do with lower atmospheric ozone that is supposedly yet another greenhouse gas.
So with lower ice coverage in the Arctic, lower atmospheric ozone should increase? And conversely, increased ice coverage in the Antarctic should see a reduction in lower atmospheric ozone.
Our Ozone hole is secured then?
Andi

Bloke down the pub
April 25, 2013 3:51 am

“We thought that the fastest and best way to understand what is happening in the Arctic was to go there and do the experiments right where the chemistry is happening,” Pratt said.
Nah, that’ll never catch on. Shirley they need computer models to confirm their findings.

RACookPE1978
Editor
April 25, 2013 3:51 am

Odd “conclusions” here about future “disasters” and projections of future Arctic ice coverages based on what was actually studied and WHEN the study was made and WHERE the study was made and HOW the proposed chemical reactions take place in the fresh snow.
They did their studies in place – which is fantastic and very rare among the CAGW-funded community of peer-challenged (er, peer-restrained) (rather, peer-reviewed) scientists.
However, they did their study and gathered their material samples off of north Alaska coast in the spring, right at the time of maximum (fresh) snow coverage over the maximum sea ice extent. Later in the summer through mid-September, there is NO sea ice in that area at all, and very little “fresh snow” over the remaining sea ice up around 80 North latitude. Given that – year-to-year – the sea ice melts and there is no fresh snow to promote their reaction over 90+ percent of the Arctic, how do they proposed their reaction takes place? Granted, since the current sea ice extent is less than it was 10 years ago, there could be a reduction in amount of reactants (compared to 10 or 25 years ago.)
But, how do they think their reaction happens all year around when there is only a small area of the Arctic “normally” covered by any sea ice, and that area has little fresh snow for so much of the year?

Bloke down the pub
April 25, 2013 3:57 am

RACookPE1978 says:
April 25, 2013 at 3:51 am
But, how do they think their reaction happens all year around when there is only a small area of the Arctic “normally” covered by any sea ice, and that area has little fresh snow for so much of the year?
As the reaction requires sunlight, I don’t think they do believe it happens all year round.

Bob
April 25, 2013 4:12 am

“Interactions between sunlight, ozone and water vapor create an “oxidizing agent” that scrubs the atmosphere of most of the pollutants human activity releases into it, Shepson said.”
I thought ozone was an oxidizing agent without needing water vapor and sunlight, it just needs to be in the presence of a “reducing agent.” I also thought that the “ozone scrubbing” action was from the creation of a free radical halogen via UV or cosmic rays, which seems to be the reverse of the description here. If it is sunlight on snow, then we depend on the major portion of this “scrubbing” to occur at minimum snow and ice? Interesting article and research, maybe they should have spent less time trying to be global warming trendy and sticking with the duller aspects of the chemistry of their research.

Alvin
April 25, 2013 4:48 am

Clearly written by or reviewed by someone with a marketing background. Note the terms “hurried” and “rush” and “balance”. And, of course, the money shot:
“In the Arctic, climate change is happening at an accelerated pace,” Pratt said. “A big question is what will happen to atmospheric composition in the Arctic as the temperatures rise and snow and ice decline even further?

Tom in Florida
April 25, 2013 4:58 am

From:
http://earthobservatory.nasa.gov/Features/ChemistrySunlight/chemistry_sunlight3.php
“Chemistry of Ozone Formation
Ozone forms readily in the stratosphere as incoming ultraviolet radiation breaks molecular oxygen (two atoms) into atomic oxygen (a single atom). In that process, oxygen absorbs much of the ultraviolet radiation and prevents it from reaching the Earth’s surface where we live.
In the language of a simplified chemical formula
When an electrically excited free oxygen atom encounters an oxygen molecule, they may bond to form ozone.
Destruction of ozone in the stratosphere takes place as quickly as formation of ozone, because the chemical is so reactive. Sunlight can readily split ozone into an oxygen molecule and an individual oxygen atom.
When an electronically excited oxygen atom encounters an ozone molecule, they may combine to form two molecules of oxygen.
The ozone formation-destruction process in the stratosphere occurs rapidly and constantly, maintaining an ozone layer. ”
Based on the above, it should be obvious that there would be less stratospheric ozone at each pole by the end of each winter because of the long period of not receiving any sunlight.

arthur4563
April 25, 2013 5:00 am

It would seem naive to assume that the Arctic will continue to warm at odds with the rest of the planet, and how can the Arctic be warming three times faster than a cooling planet?

Richdo
April 25, 2013 5:18 am

Paper is paywalled, too bad, it would be interesting to read what they actually did.
http://www.nature.com/ngeo/journal/vaop/ncurrent/full/ngeo1779.html#supplementary-information
From the Supplementary Info, http://www.nature.com/ngeo/journal/vaop/ncurrent/extref/ngeo1779-s1.pdf, it appears that they performed no measurements of bromine with sea water/dark/sunlight to compare with the various snow/dark/sunlight data. So how can they draw any conclusions about the impact of “loss of sea ice”.
I really hate this “science” by press release. It has more to do with marketing than science.

Steve Keohane
April 25, 2013 5:29 am

William McClenney says:April 25, 2013 at 12:10 am
Yes, IIRC correctly, good things come from Uranus Corporation. If you are referencing ‘The Groove Tube’, you’re probably getting on as I am.

tadchem
April 25, 2013 5:56 am

The ozone layer has been alternately thinning AND swelling with the seasons as long as measurements have been made – with stochastic perturbations to the cycle. Only a myopic idiot would assume that the ozone layer had been ‘stable’ before we started looking at it or before we started using CFCs, and only an anthropocentric narcissist would assume that humans were completely responsible for the cycle – or even for the perturbations.
With apologies to Dire Straits I sing: “I want my … I want my … I want my CFCs!”

Jim Cripwell
April 25, 2013 6:01 am

I like this study from the NSF, because they did hands-on empirical measurements and experiments to make the determination – Anthony
What a sad reflection of the state of science brought on by the unscientific attitudes of the RS, the APS and the NSF on the subject of CAGW. Our host congratulates the authors for finally doing what the scientific method demands. I am sure Galileo and Newton are turning in their graves.

Myron Mesecke
April 25, 2013 6:58 am

phlogiston says:
April 25, 2013 at 12:43 am
What is happening to stratospheric ozone at present? I have noticed in our recent very brief sunny interlude in our late 2013 spring, that several people including myself went red / brown quite quickly after a few minutes or hours in the sunlight. A purely anecdotal observation but is there any thinning of ozone in the NH?
Late 2013 Spring. That’s the key. You and those several other people have spent a longer time than usual out of the sun due to the longer than usual period of cold weather. So your skin has lost more of its previous tan. Your skin was paler and therefore more sensitive to sunlight. So you tan or burn more easily when you finally were able to get some sun.
My daughter made a similar comment when track season started up. She couldn’t believe that she could burn so easily. I told her that she had been out of the sun all winter so that first amount of sun had more effect. She said, “That makes sense.”

Jeff Alberts
April 25, 2013 7:01 am

The new research also indicates that the surface snowpack above Arctic sea ice plays a previously unappreciated role in the bromine cycle and that loss of sea ice, which been occurring at an increasingly rapid pace in recent years, could have extremely disruptive effects in the balance of atmospheric chemistry in high latitudes.

So they still think they entire planet was static until the last 50 years or so. Stupid.

MinB
April 25, 2013 7:13 am

“…the compound was most prevalent over snow-covered first-year sea ice and tundra”
What does this statement mean? Most prevalent compared to what? To open water? To snowless tundra? Or to sea ice older than first year?
If the latter, why would the age of the ice make a difference if it’s the snow on top that is interacting? Maybe the full paper clarifies this. It would seem to me that MORE sea ice melting would lead to MORE first-year sea ice the following freeze season and MORE cleansing.

DesertYote
April 25, 2013 8:29 am

Jens Bagh says:
April 25, 2013 at 3:09 am
What is the origin of the Bromine in the snow and how did it get there?
###
Seawater.

higley7
April 25, 2013 8:42 am

HOwever, as cold air sinks and flows Southward, it is unlikely that this bromine, so plentiful near the surface, makes it to the upper atmosphere and interacts with ozone up there. WHat occurs at the surface could more likely be unrelated to what occurs up there. SOrry, guys.
The credibility of this work leaves the building as soon as they claim the increasing loss of Arctic ice. “occurring at an increasingly rapid pace in recent years” Just not happening.

April 25, 2013 10:12 am

Dave Wendt says: April 25, 2013 at 12:08 am
Re your comment about Arctic ice rebound: not only does Arctic ice rebound, the long-term loss is not over the complete Arctic, but more focused in the eastern sub-ocean areas. I’ve wondered how much loss is reasonable as an excuse for European winters when the loss is neither “global” nor for all winter. Also:
The loss of sea-ice and therefore snow cover occurs during only part of the lighted time in the Arctic. What we need is the portion of the sea-ice and snow loss during the lighted part when the sunlight-induced action occurs to see the proportional magnitude of the change. Regardless:
Whatever the change, an increase in low-level ozone occurs that reduces air pollution in the lower levels. The proportional increase may be large if the bromine historically has been killing the ozone. So we might have a significant POSITIVE benefit to reduced Arctic ice.
Who woulda thunk it.

April 25, 2013 10:12 am

“…Temperatures at the poles are too cold for the existence of much water vapor and in the Arctic this cleaning process appears instead to rely on reactions on frozen surfaces involving molecular bromine, a halogen gas derived from sea salt…”

Which leaves me very puzzled about the Bromine phase transitions and chemical interaction levels in that temperature range. especially given an abundance level approximately 1-2 PPTv (‘Parts per Trillion by Volume’) for Bromine. Bromine would be a solid at the temperatures involved at their location. Bromine MonOxide (BrO) might be gaseous, though I couldn’t quickly locate that info on the web.
Also given that BrO quite happily reacts with O2 and BrO, I’m not sure much of that minute 1-2 PPTv amount of BrO makes it up to the Ozone O3 level. I wonder if their experiment identified the specific chemical reactions, reaction initiation, energy sources, energy transfers and all. I did read in their blurb about the Arctic air freely circulating, so I have dim hopes that they’ve quantified for initiating and exiting components with all energy gains/losses. Surmising chemical activity within hidden ice crystal structures should be a neutral statement if the research is earnest..
Add to that, that there is more than enough Chlorine to put Bromine as the minor player in the magic mystery ozone disappearance.
Next on the puzzle me thoroughly list is why fixate on Bromine as the magic mystery player causing the ozone layer to take a flyer. Now if the research is strictly on BrO formation and the alarm words are PR ‘Jazz it up’ stuff then there is hope for good research. If this looking for the bit player to bolster alarmist ‘man is destroying our ozone levels’, then I wouldn’t expect much.

Duster
April 25, 2013 10:46 am

It seems unlikely that the effect is significant in Antarctica since the release of Bromine is correlated with first-year sea ice.

otsar
April 25, 2013 11:01 am

Why study only Bromine and not the other Halogens? Did they know they might discover someting very inconvenient?
I have analysed many metal surfaces that have been exposed to the environment using AES and XPS. In a lage number of samples I have found 1 to 2% atomic concentration in the top 60 Angstrom.
I hope they used Bromine free PMMA for the top window in their enclosure and other parts. Bromine is used as a fire retardant in many plastics. It is used from electronics packaging to clothing.

otsar
April 25, 2013 11:04 am

OOPS
In the top 60 Angstrom I have found Cl.

richardscourtney
April 25, 2013 11:08 am

Duster:
The article reports Kyle Custard saying:

“Sea ice had been thought to be the source of the gaseous bromine,” she said. “We had an ‘of course!’ moment when we realized it was the snow on top of the sea ice. The snow is what is in direct contact with the atmosphere. Sea ice is critical to the process, though. Without it, the snow would fall into the ocean, and this chemistry wouldn’t take place. This is among the reasons why the loss of sea ice in the Arctic will directly impact atmospheric chemistry.”

But your post at April 25, 2013 at 10:46 am says in total

It seems unlikely that the effect is significant in Antarctica since the release of Bromine is correlated with first-year sea ice.

Please explain the source of your “correlation” which is a direct contradiction of the statement I quote from Custard.
Richard

tz2026
April 25, 2013 11:59 am

No! It is because people several hundred miles away are spraying their aerosol cans! Releasing chemicals whose patents are about to expire into the atmosphere so must be banned.