High levels of molecular chlorine found in Arctic atmosphere

From the Georgia Institute of Technology

Scientists studying the atmosphere above Barrow, Alaska, have discovered unprecedented levels of molecular chlorine in the air, a new study reports.

Molecular chlorine, from sea salt released by melting sea ice, reacts with sunlight to produce chlorine atoms. These chlorine atoms are highly reactive and can oxidize many constituents of the atmosphere including methane and elemental mercury, as well activate bromine chemistry, which is an even stronger oxidant of elemental mercury. Oxidized mercury is more reactive and can be deposited to the Arctic ecosystem.

The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.

“No one expected there to be this level of chlorine in Barrow or in polar regions,” said Greg Huey, a professor in the School of Earth and Atmospheric Sciences at the Georgia Institute of Technology in Atlanta.

The study was published January 12 in the journal Nature Geoscience and was supported by the National Science Foundation (NSF), part of the international multidisciplinary OASIS program.

The researchers directly measured molecular chlorine levels in the Arctic in the spring of 2009 over a six-week period using chemical ionization mass spectrometry. At first the scientists were skeptical of their data, so they spent several years running other experiments to ensure their findings were accurate.

The level of molecular chlorine above Barrow was measured as high as 400 parts per trillion, which is a high concentration considering that chlorine atoms are short –lived in the atmosphere because they are strong oxidants and are highly reactive with other atmospheric chemicals.

Molecular chlorine concentrations peaked in the early morning and late afternoon, and fell to near-zero levels at night. Average daytime molecular chlorine levels were correlated with ozone concentrations, suggesting that sunlight and ozone may be required for molecular chlorine formation.

Previous Arctic studies have documented high levels of oxidized mercury in Barrow and other polar regions. The major source of elemental mercury in the Arctic regions is coal-burning plants around the world. In the spring in Barrow, ozone and elemental mercury are often depleted from the atmosphere when halogens — chlorine and bromine — are released into the air from melting sea ice.

“Molecular chlorine is so reactive that it’s going to have a very strong influence on atmospheric chemistry,” Huey said.

Chlorine atoms are the dominant oxidant in Barrow, the study found. The area is part of a region with otherwise low levels of oxidants in the atmosphere, due to the lack of water vapor and ozone, which are the major precursors to making oxidants in many urban areas.

In Barrow, snow-covered ice pack extends in every directly except inland. The ultimate source of the molecular chlorine is the sodium chloride in sea salt, Huey said, most likely from the snow-covered ice pack. How the sea salt is transformed into molecular chlorine is unknown.

“We don’t really know the mechanism. It’s a mystery to us right now,” Huey said. “But the sea ice is changing dramatically, so we’re in a time where we have absolutely no predictive power over what’s going to happen to this chemistry. We’re really in the dark about the chlorine.”

Scientists do know that sea ice is rapidly changing, Huey said. The sea ice that lasts from one winter to the next winter is decreasing. This has created a larger area of melted ice, and more ice that comes and goes with the seasons. This seasonal variation in ice could release more molecular chlorine into the atmosphere.

“There is definite climate change happening in the Arctic,” Huey said. “That’s changing the nature of the ice, changing the volume of the ice, changing the surface

###

High levels of molecular chlorine in the Arctic atmosphere

Liao et al, Nature Geoscience (2014) doi:10.1038/ngeo2046

Abstract

Chlorine radicals can function as a strong atmospheric oxidant1, 2, 3, particularly in polar regions, where levels of hydroxyl radicals are low. In the atmosphere, chlorine radicals expedite the degradation of methane4, 5, 6 and tropospheric ozone4, 7, and the oxidation of mercury to more toxic forms3. Here we present direct measurements of molecular chlorine levels in the Arctic marine boundary layer in Barrow, Alaska, collected in the spring of 2009 over a six-week period using chemical ionization mass spectrometry. We report high levels of molecular chlorine, of up to 400 pptv. Concentrations peaked in the early morning and late afternoon, and fell to near-zero levels at night. Average daytime molecular chlorine levels were correlated with ozone concentrations, suggesting that sunlight and ozone are required for molecular chlorine formation. Using a time-dependent box model, we estimate that the chlorine radicals produced from the photolysis of molecular chlorine oxidized more methane than hydroxyl radicals, on average, and enhanced the abundance of short-lived peroxy radicals. Elevated hydroperoxyl radical levels, in turn, promoted the formation of hypobromous acid, which catalyses mercury oxidation and the breakdown of tropospheric ozone. We therefore suggest that molecular chlorine exerts a significant effect on the atmospheric chemistry of the Arctic.

About these ads

122 thoughts on “High levels of molecular chlorine found in Arctic atmosphere

  1. “How the sea salt is transformed into molecular chlorine is unknown.”

    But I am sure they will find a way to make it our fault, create an expensive government program to mitigate it, and in the process shovel billions of dollars to political supporters who get into the “whatever is causing the chlorine” business.

  2. How did this pass peer-review when the abstract mixes the terms chlorine radicals and molecular chlorine? I assume they mean atomic chlorine when they they chlorine radicals which is more reactive Molecular chlorine away from water is pretty chemically stable. Metals don’t react with it. I doubt organic material would either at any appreciable rate.

  3. They already did make it our fault. It was the chlorine in the polar regions which was caused by CFCs in refrigerants which caused the ozone hole. Then we phased out CFCs years ago, so there might be some explaining to do about the new chlorine.

  4. But, but, there shouldn’t be any chlorine up there because we banned chlorofluorocarbons to save the ozone hole. Or something like that.

    When they did up the feel-good Montreal Protocol, did they consider the contribution of sea salt to atmospheric chlorine? Don’t know, but kinda doubt it.

  5. “We don’t really know the mechanism. It’s a mystery to us right now,”
    Molecular chlorine, from sea salt released by melting sea ice…
    _________________
    Beg your pardon- sea salt released from MELTing ice?
    You should have stuck with the “we’re clueless” part.

    You guys must have been listening to the “scientists” abourd the Akademik Shokalsiy, because one of them said that melting ice caused salt release which caused the ice to freeze and trap them in place and turn them into buffoons.
    Oh, Nevermind. I get it. You’re making your bid to be buffoons, too.

  6. “The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.”

    Its the first time its been measured and its the first time such high levels have been measured…

    Just a thought: if its the ‘first time’ they have been measured how in the world can you say ‘such high levels’???

    I guess its good enough for climate science

  7. Huh! “No one expected there to be this level of chlorine in Barrow or in polar regions,” About 4 years ago, when I began to look into CAGW and the Antarctic Ozone Depletion Area, I recalled sailing in the lower parts of the Roaring Forties and the accumulation of salt salt spray high up on the ships. I also noticed a correlation between the circumpolar lows and the Antarctic Ozone Depletion Area. I expressed views that there could be a connection on a facebook site
    , but was ridiculed……

  8. Molecular chlorine, from sea salt released by melting sea ice, reacts with sunlight to produce chlorine atoms”

    Er, I’m not sure if they know that sea salt in salty water (of which there is quite a lot in the ocean anyway, without having to invoke melting sea ice) does not spontaneously yield molecular chlorine.

    Climate science: they make it up as they go along.

  9. 400 parts per trillion is not high. I am presuming that trillion means 10^12 so 4 CL atoms to 10^10 other atoms and molecules. Nope not high at all.

  10. Steve (Paris) says atJanuary 15, 2014 at 12:42 am…

    The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.

    Well, that could mean that molecular chlorine has been measured in the atmosphere in places other than the Arctic.
    In which case the study could be finding that cold places – with little sunlight – are less efficient at breaking up molecular chlorine.
    That would be a helpful and believable observation. Indeed it is not unexpected
    .

  11. ““No one expected there to be this level of chlorine in Barrow or in polar regions,” said Greg Huey, a professor in the School of Earth and Atmospheric Sciences at the Georgia Institute of Technology in Atlanta.”

    So, something never directly measured before was measured and the result exceeded expectations of this professor? Clearly the scientific method was AWAL during this study.

  12. Molecular chlorine released by melting sea ice? Sea ice melts from below sea level, no? How does that chlorine get released into the atmosphere considering it would exist as hypochlorite in ice and seawater?

  13. So all this was found in 2009 and has been analyzed for the past four years, You’d think these folks would e interested enough to return to see what’s going on now, four years later. They
    don’t seem to be very inquisitive about something they .say surprised them. Also lots and lots of “we don’t knows” and, in the end, a lack of words about what, if anything, this all means, if it
    means anything.

  14. The sea ice is changing dramatically they opine, there is less of it every year they say. Except that it has been increasing every year. They are pretending they are in the arctic, they best be careful one of those southern polar bears may get them.

    They do not know what is causing it but it only happens during the day, it must be the penguins.
    Simple lab experiment using the different frequencies of the electro magnetic spectrum would most likely give them a clue. They seem to be about as clued up as the ship of fools.

    As for the traces of mercury down there, no one eats penguins except sea lions. Given enough time it may be a mineable resource.

  15. The major source of elemental mercury in the Arctic regions is coal-burning plants around the world.

    Yeah? How can they be so sure of that? What’s their basis for this claim? How about all the naturally burning coal seams?

  16. I remember that in the early days of atomic absorption spectroscopy someone published a list of metals found in a potato. The list included numerous highly toxic heavy metals and the story made headlines in the press. The quantities involved were negligible so in a way it was a story about (almost literally) nothing.

    This story sounds fairly similar.

  17. At high school in Tønsberg (Norway) in 1962, in the chemistry course, we titrated for free chlorine in sea water samples from different places in the Oslo fjord. At that time, we were taught that free chlorine was generated by the action of UV light on sea water.

    I have tried to trace this information at some occasions (being once responsible for the follow-up of dioxins in the environment of interest to the Norwegian dairy industry), but failed to find any hard facts. Are there better chemists than myself reading this, so please come forward!

  18. These chlorine atoms are highly reactive and can oxidize many constituents of the atmosphere including methane and elemental mercury . . . .

    Would this be a significant amount?

  19. Be afraid, be very afraid. The arctic has been doing this for millions of years. Be afraid. Oh and send us some money so we can find out how this might happen.

  20. “Molecular chlorine, from sea salt released by melting sea ice” Did they really say this?
    When water freezes it excludes solute (salts) from its crystal matrix. The surrounding seawater gets more salty and denser an so sinks- which drives the thermoHALINE circulation.
    And these bozos got published in Nature??

  21. ‘average, and enhanced the abundance of short-lived peroxy radicals. Elevated hydroperoxyl radical levels, in turn, promoted the formation of hypobromous acid, which catalyses mercury oxidation and the breakdown of tropospheric ozone.’
    I’m having trouble with this.
    The ‘box model’ presumably put Cl2, OH-, CH4, CO2,H2O Br-, Cl- and a shot of O3 plus UV and Hg, in a mathematical model which gained a result.
    What are the chemical reactions?
    At what level of the atmosphere do they occur and at what temperature and pressure?
    Could the reference of melting ice releasing Cl and Br refer to permafrost or the breakup of sea ice to allow the formation of sea spray as suggested by ‘The Ol’ Seadog.’ says:
    January 15, 2014 at 12:53 am
    Intuitively I can’t see peroxides lasting long enough in cold seawater to push an equilibrium to hypobromous acid. If by luck any hypobromous acid were produced it would spontaneously disassociate any way as it is highly unstable.
    Using a peroxidase to produce hydrobromous acid in a cell at 37c consumes a third of the energy requirements of the cell.Using its organelles the cell mobilises the reactions.
    This drives the reaction. Interactions are not random.
    Its hard to see anything being left to catalyze mercury oxidation in the atmosphere once the peroxidase and hydrobromic acid had fallen apart.

  22. One has measured a lot of chlorine (under form of chloride) at a lot of places, usually higher with winds from the seaside than from land side.
    The main background indeed is caused by the oceans: not the melting sea ice, which is largely salt/chlorine free, but the open oceans which present a larger surface if the ice melts. Sea salt spray may be one source, but the Na-Cl bond is hard to split, as it needs a lot of energy. Alternative is HCl (hydrochloric acid) which evaporates from the ocean surface, even if the ocean waters are slightly alkaline, because it is a volatile molecule. The global emissions from that source are estimated at 300,000 tons per year:

    http://volcano.oregonstate.edu/education/gases/man.html

    Human and volcanic contributions completely dwarfed by the ocean releases…

    HCl may rain out, but if precipitation is low, as is the case at Barrow, it remains longer in the atmosphere. It is easier to split in the atmosphere by UV sunlight than NaCl (common salt).

    Another, much larger source is CH3Cl, methylchloride or chloromethane, also 99% natural, made by fungi in their chemical pathway to make strong chemicals that are capable of cracking lignin, the chaotic structures that make the glue which binds cellulose together in all plants. Fungi need the cellulose as energy food, but lignin stands in the way.
    While most algue are minor sources, some of the main species found in the Arctic (including red algue in snow) are interesting sources:

    http://en.wikipedia.org/wiki/Methyl_chloride

    An extensive study of 30 species of polar macroalgae revealed the release of significant amounts of CH3Cl in only Gigartina skottsbergii and Gymnogongrus antarcticus.[
    But the main source is the production of methylchloride by fungi:

    http://aem.asm.org/content/64/8/2831.full

    Most of the methylchloride is split up in the troposphere under UV light and the free chlorine radicals help to destroy a lot of organics in the troposphere, together with OH radicals, also made by UV light from water molecules. But because of the quantities involved, some may even reach the stratosphere, adding to ozone depletion, in this case an all natural cause…

    So, in my opinion, the origin of the free chlorine is largely known, and probably more from the increased metabolism via the methylchloride route than from the salt/HCl route…

  23. Ferdinand Engelbeen:

    I write to draw attention to your excellent post at January 15, 2014 at 2:10 am and especially your final paragraph.

    Richard

  24. How the sea salt is transformed into molecular chlorine is unknown

    If you haven’t identified the mechanism, how did you know the source?

  25. @- Katherine
    ‘The major source of elemental mercury in the Arctic regions is coal-burning plants around the world.’
    Yeah? How can they be so sure of that? What’s their basis for this claim? How about all the naturally burning coal seams?

    All this information is in the public domain and accessible with a quick web search.
    Naturally burning coal seams are at most around 2% of all the coal burnt.
    Mercury from burning coal has more than doubled the natural level of mercury in the environment, it is identiifable from the isotopic ratios.

    http://www.ncbi.nlm.nih.gov/pubmed/22103560

    Incidentally the molecular chlorine measured in this research has absolutely nothing to do with ozone depletion from CFCs in the polar stratosphere. It is far too reactive and water soluble to get out of the lower troposphere.

  26. Back when I was in the industry we used to call this type of thing ‘pushing buttons’.
    The buttons being pushed here are clearly marked Arctic, Chlorine and Mercury.
    A successful paper pushes the right buttons to get published and a successful press
    releases the idea into the MSM.
    Warmists have been exploiting this technique since the very beginning.

  27. Katherine says:
    January 15, 2014 at 1:33 am

    The major source of elemental mercury in the Arctic regions is coal-burning plants around the world.

    That may be the main human source, but the main source in The Netherlands is measured as natural evaporation from deeper earth layers. The natural gas wells also are contaminated with a lot of mercury that need to be bounded with sulphur to get it out of the gas. That makes the largest deposit of mercury containing solid waste in The Netherlands…
    So I wonder how much atmospheric mercury in the Arctic is of natural origin and how much is human made…

  28. Ice contains essentially no salt. What are they talking about?

    Anyone can do the experiment, even Al Gore: put some salt water in the freezer. When a little ice forms, remove it, rinse it off, and taste it.

  29. Logic check:

    This is the first time molecular chlorine has been measured in the Arctic.
    (OK)

    The level of molecular chlorine was as high as 400 parts per trillion.
    (An amount so miniscule it’s extremely hard to measure accurately.)

    These levels are ‘unprecedented’.
    (Wrong. You just said they’ve never been measured before. There is no data for comparison.)

    “We don’t really know the mechanism. It’s a mystery to us..,”
    (OK, time to apply the scientific method.)

    “But the sea ice is changing dramatically”… “There is definite climate change happening in the Arctic”… Conclusion: it’s from sea salt released by melting sea ice.
    (FAIL!)

    These are not scientists. These are climate clowns.

  30. Ferdinand Engelbeen says:
    January 15, 2014 at 2:10 am
    “Another, much larger source is CH3Cl, methylchloride or chloromethane, also 99% natural, made by fungi in their chemical pathway to make strong chemicals that are capable of cracking lignin, the chaotic structures that make the glue which binds cellulose together in all plants. Fungi need the cellulose as energy food, but lignin stands in the way.”

    THANKS Ferdinand!!!

  31. Trygve Eklund says:
    January 15, 2014 at 1:48 am

    At high school in Tønsberg (Norway) in 1962, in the chemistry course, we titrated for free chlorine in sea water samples from different places in the Oslo fjord. At that time, we were taught that free chlorine was generated by the action of UV light on sea water.

    Interesting to see that, never thought it would happen in seawater too, as it should get extremely fast reacting with organics always present in seawater…
    I was heavily involved in dioxin chemistry too, as working in a chlorine/PVC factory which was accused of high dioxin emissions, without a shred of evidence: it were the badly designed waste burning facilities which were the main source.
    Dioxin formation also is a radical reaction where metals, especially copper, catalyse the transformation of chloride into chlorine radicals, which form dioxins in the temperature range of 300-600°C. The total amount of chloride is quite unimportant, but copper amounts and temperature are. Above the temperature range, dioxins are destroyed and below that the formation is too slow.
    The design of the waste burning ovens nowadays is maintaining at least 800°C and fast cooling by quenching past the dioxin formation temperature range…
    I had some contact with the Norsk Hydro PVC plant in Porsgrunn, not so far from Tønsberg and still have regular contact with friends in Krokstadelva, first met on top of the Galdhøpiggen in 1976…

  32. As others have alluded to, how do they know it hasn’t always been like it, or at least for many hundreds or thousands of years?

  33. Can chlorine oxidize? Or does oxidization have to involve oxygen?

    Sometimes the reporters make the scientists look like dopes. It is just one of those things scientists have to endure, to get funding.

    Sea spray also liberates trace amounts of fluorine, bromine and iodine. Any element ending in “ine” reacts with ozone in the upper atmosphere, and big storms can suck sea spray right up past the tropopause into the stratosphere. Ozone holes may well be caused by sea spray.

  34. Given they simply don’t know what is going on would the fact they jumped on ‘climate change ‘ as the cause be becasue there is still buckets of funded avaiable to support ‘the cause ‘ and by doing this thay stated to others in ‘the team’ their true believers credentials ?

  35. If this is the first time that elemental chlorine has been measured then how can they claim that measured volumes are ”unprecidented”? It may be normal and happen every year during spring melt.
    Another ”scare” we will end up paying for.

  36. Steve (Paris) 12:42. I am glad I read through the comments, before commenting, because I thought the exact same thing. The only time that they have measured, so they have no idea if this is an unusually high reading for that location, they have no idea how it is formed, so actually have no idea if it has anything to do with melting sea ice or not. This whole thing is a massive pile of work which can be summerised as

    “nope, we don’t know jack about what’s happening, or if it is unusual or not, but I need my grant extending, so I’ll blame melting sea ice”

  37. @- Ferdinand Engelbeen
    “So I wonder how much atmospheric mercury in the Arctic is of natural origin and how much is human made…”

    Given that at least half of the background mercury levels we measure are human made, that is that anthropogenic sources have doubled the natural background level, {Munthe et al 2001} at least half the mercury measured anywhere must be from human activity releasing it from natural sequestration.

  38. The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.

    Has there always been “high levels of molecular chlorine in the atmosphere” above Barrow, Alaska?

    And now onto related news.

    BBC – 15 January 2014
    “Australia heatwave prompts fire alerts”

    http://www.bbc.co.uk/news/world-asia-25723867

    Last year was recently declared Australia’s hottest on record, further raising questions about the impact of climate change, our correspondent adds.

    Get ready for “it’s a sure sign of global warming,” “the dice is loaded” blah, blah.

  39. It’s good to see that some people have been keeping an eye on chlorine in the air over Barrow since at least 1965.

    Iodine, bromine, and chlorine in winter aerosols and snow from Barrow, Alaska
    Robert A. Duce, John W. Winchester, Theodore W. Van Nahl

    Abstract

    Iodine, bromine, and chlorine have been determined in atmospheric aerosols and in snow collected in Barrow, Alaska, during January, 1965, by means of neutron activation analysis. Aerosols collected using both an aircraft collector by impaction and a ground-based 1.0 ? Type EA Millipore filter collector show concentrations of Cl to be much more variable than either Br or I, and I/Br points cluster at 0.1-0.2 gI/gBr for the filter samples. Cl varies from <0.02 to 4 ?g Cl/m3STP in the filter samples, and the aircraft concentrations agree with those taken by filter on the same days. Filter Br is 1–30 ngBr/m3STP and I is 0.3–10 ngI/m3STP, and the ratios I/Cl and Br/Cl increase sharply with decreasing Cl. Snow samples from the ground have Br/Cl somewhat greater than in sea water, although all halogen concentrations decrease with increasing distance from the sea up to 10 km. Assuming a mixture of undifferentiated sea salt and a more permanent atmospheric component, we estimate for the atmospheric component in the snows I/Br?0.2. Sea water, sea ice, and related samples were analyzed, and I/Cl = 4 times 10?6 gI/gCl is normal for sea water, although Br/Cl = 3.8 times 10?3 gBr/gCl stands a little high.

    http://www.tellusa.net/index.php/tellusa/article/view/9630

    http://onlinelibrary.wiley.com/doi/10.1111/j.2153-3490.1966.tb00232.x/pdf

    DOI: 10.1111/j.2153-3490.1966.tb00232.x

  40. The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.

    Here is another also reporting on high concentrations of molecular chlorine off Long Island. What mechanism could have caused this? Any chemists in the house?

    Letters to Nature – Accepted 27 April 1998
    Unexpectedly high concentrations of molecular chlorine in coastal air
    C. W. Spicer1 et al
    …..Here we report night-time observations of molecular chlorine concentrations at a North American coastal site during onshore wind flow conditions that cannot be explained using known chlorine chemistry. The measured Cl2 mixing ratios range from <10 to 150 parts per 1012 (p.p.t.), exceeding those predicted5 for marine air by more than an order of magnitude. Using the observed chlorine concentrations and a simple photochemical box model, we estimate that a hitherto unrecognized chlorine source must exist that produces up to 330 p.p.t. Cl2 per day. The model also indicates that early-morning photolysis of molecular chlorine can yield sufficiently high concentrations of chlorine atoms to render the oxidation of common gaseous compounds by this species 100 times faster than the analogous oxidation reactions involving the OH radical, thus emphasizing the locally significant effect of chlorine atoms on the concentrations and lifetimes of atmospheric trace species in both the remote marine boundary layer and coastal urban areas.
    Nature 394, 353-356 (23 July 1998) | doi:10.1038/28584;

    http://www.nature.com/nature/journal/v394/n6691/abs/394353a0.html

    Tables and graphics

    http://www.nature.com/nature/journal/v394/n6691/fig_tab/394353a0_T1.html

    http://www.nature.com/nature/journal/v394/n6691/fig_tab/394353a0_ft.html

  41. izen:

    I am bothering to answer your daft post at January 15, 2014 at 3:25 am to avoid any possibility of uninformed onlookers being misled by your nonsense.

    @- Ferdinand Engelbeen
    “So I wonder how much atmospheric mercury in the Arctic is of natural origin and how much is human made…”

    Given that at least half of the background mercury levels we measure are human made, that is that anthropogenic sources have doubled the natural background level, {Munthe et al 2001} at least half the mercury measured anywhere must be from human activity releasing it from natural sequestration.

    No, izen. It does not follow that the background level of mercury must be at least half from human activities EVERYWHERE merely because Munthe et al determined that is the case where they assessed it (even if Munthe et al were right). And the above report is about the Arctic region which had not been assessed before.

    If you had a rational argument to refute Ferdinand then you would have provided it and not the nonsense you have.

    I provide this link to Ferdinand’s fine post help those who missed it

    http://wattsupwiththat.com/2014/01/15/high-levels-of-molecular-chlorine-found-in-arctic-atmosphere/#comment-1536483

    Richard

  42. Natural mining (glaciation) is you biggest source of mercury. When you grind rock you get lots of heavy metals.

  43. Meanwhile in the Antarctic:

    “We have just pulled up the anchor and are sailing out of Newcomb Bay having completed the Casey Resupply. We had 5 barge trips of cargo to come on board to load the final RTA cargo. Loaded the Navy boat and barge on board and prepared for sea. We departed at 1.05pm with everyone happy to be on our way. I wish to thank the crew of the Aurora Australis, the Casey Station Leader, the Casey shore based crews and the expeditioners on station and on board for making this a successful resupply. As mentioned in previous sitreps it takes a large number of people working in synch with each to make a resupply happen safely and successfully. Tonight we are all looking forward to a barbecue on the trawl deck. To have a bbq whilst sailing past icebergs is a unique and quite surreal experience. Cheers Leanne and Mark”

    No Hobart ETA yet.

  44. Jimbo: “”Cl varies from <0.02 to 4 ?g Cl/m3STP in the filter samples""

    Any idea what "in the filter samples" means?

    If "?g" is nanograms, then my calculator says (4 x 10^-9) / (1.2 x 10 ^ 3) * 29 / 71 = 1.4 x 10^-12, i.e., 1.4 parts per trillion, more than two orders of magnitude less than the 400 parts per trillion reported by the paper to which the top post is directed.

  45. Michael says:
    January 15, 2014 at 12:22 am

    How did this pass peer-review when the abstract mixes the terms chlorine radicals and molecular chlorine? I assume they mean atomic chlorine when they they chlorine radicals which is more reactive Molecular chlorine away from water is pretty chemically stable. Metals don’t react with it. I doubt organic material would either at any appreciable rate.

    Chlorine atoms are chlorine radicals. When you photolyze a chlorine molecule you get two neutral chlorine atoms which, because they each have an unpaied elecron, are radicals.

  46. @- richardscourtney
    “It does not follow that the background level of mercury must be at least half from human activities EVERYWHERE ….If you had a rational argument to refute Ferdinand then you would have provided it and not the nonsense you have.
    I provide this link to Ferdinand’s fine post help those who missed it”

    If you had read the comment you link to carefully you would have seen that Ferdinand was discussing chlorine NOT mercury.

  47. In re Millipore filters, are commonly used to measure insoluble (metal) content by filtering aliquot and weighing provides mass/mass fraction. In later practice, visual density comparison suffices for maintenance. So it depends on the sampled and filtered volume.

  48. Yeah, Right.

    Are these folks complete idiots? Or do they just think we are?

    There are VOLCANOES, active volcanoes up there. October 10, 2013 Kliuchevskoi eruption continues – column of ash up to 5.3 km, Kamchatka

    Kliuchevskoi is Kamchatka’s highest and most active volcano. Since its origin about 6000 years ago, the beautifully symmetrical, 4835-m-high basaltic stratovolcano has produced frequent moderate-volume explosive and effusive eruptions without major periods of inactivity…. There are more than 150 volcanoes on Kamchatka and up to 30 of them are active.

    There are even active volcanoes under the sea. Arctic Volcanoes Found Active at Unprecedented Depths

    Volcanoes cause climate gas concentrations to vary
    First comprehensive analysis of sulfur dioxide concentration in the stratosphere/10 years. Measurements on board of ENVISAT/no identifiable anthropogenic sources of sulfur dioxide.

    Trace gases and aerosols are major factors influencing the climate. With the help of highly complex installations, such as MIPAS on board of the ENVISAT satellite, researchers try to better understand the processes in the upper atmosphere….

    The increase in the stratospheric aerosol concentration observed in the past years is caused mainly by sulfur dioxide from a number of volcano eruptions. “Variation of the concentration is mainly due to volcanoes,” Höpfner explains….

    Volcanic Gases and Their Effects

    Magma contains dissolved gases that are released into the atmosphere during eruptions. Gases are also released from magma that either remains below ground (for example, as an intrusion) or is rising toward the surface. In such cases, gases may escape continuously into the atmosphere from the soil, volcanic vents, fumaroles, and hydrothermal systems….

    The most abundant gas typically released into the atmosphere from volcanic systems is water vapor (H2O), followed by carbon dioxide (CO2) and sulfur dioxide (SO2). Volcanoes also release smaller amounts of others gases, including hydrogen sulfide (H2S), hydrogen (H2), carbon monoxide (CO), hydrogen chloride (HCL), hydrogen fluoride (HF), and helium (He).….

    The chart in the article shows SO2 as number 3 after H2O and CO2, as much as 11% of the gases depending on the volcano. HCl can be as much as 3%.

    Also see blog article: Volcanoes Belch Chlorine

    A thanks to Dr. Art Robinson who mentioned Cl and volcanoes and ozone holes many many years ago when the taking of samples was done down wind of an active volcano and mankind was blamed for the pollution and ozone hole. The lying in politicized science has been going on for years.

  49. izen:

    At January 15, 2014 at 6:12 am you say to me

    If you had read the comment you link to carefully you would have seen that Ferdinand was discussing chlorine NOT mercury.

    And if your brain were made of dynamite it would not be sufficient to blow your hat off. So what?

    Richard

  50. Katherine says: @ January 15, 2014 at 1:33 am

    Yeah? How can they be so sure of that? What’s their basis for this claim? How about all the naturally burning coal seams?
    >>>>>>>>>>>>>
    Not to mention from the land. Cinnabar is a mercury containing rock (ore) that has been mined for ~5000 or more years. Erosion of the rock puts the mercury into the sea.

    Mercury
    …Natural sources of mercury include volcanoes, hot springs, and natural mercury deposits….

    Mercury occurs in various forms and compounds in the environment, some of which are not bioavailable…. Methyl mercury is readily taken up by aquatic organisms and tends to concentrate as it moves up the food chain. This process is referred to as biomagnification and can result in high mercury concentrations in predatory fish such as striped bass and sharks, and in fish eating birds and mammals….

    http://www.conservation.ca.gov/cgs/minerals/hazardous_minerals/mercury/Pages/index.aspx

    …Several forms of mercury occur naturally in the environment. The most common natural forms of mercury found in the environment are metallic mercury, mercuric sulfide (cinnabar ore), mercuric chloride, and methylmercury. Some microorganisms (bacteria and fungi) and natural processes can change the mercury in the environment from one form to another. The most common organic mercury compound that microorganisms and natural processes generate from other forms is methylmercury. Methylmercury is of particular concern because it can build up or biomagnify in certain edible freshwater and saltwater fish and marine mammals to levels that are many times greater than levels in the surrounding water.

    http://www.eoearth.org/view/article/154567/

    Also see WUWT: Mercury, the Trickster God by Willis.

  51. Ferdinand Engelbeen says:

    Did you mean Chlorine – VCM – PVC? with a butadiene inhibitor for bulk shipment of the VCM?

  52. I see from the photo at the press release that at least one of the instruments used by these researchers was attached directly to plywood. Any chance that part of their chlorine measurement resulted from emissions from the plywood?

  53. izen says: @ January 15, 2014 at 3:25 am

    ….Given that at least half of the background mercury levels we measure are human made…
    >>>>>>>>>>>>>
    Izen humans don’t MAKE elements unless you are talking nuclear reactions. Like every other living thing we concentrate the elements/ molecules that are useful to us. We are just a heck of a lot more inventive compared to fungi or termites.

    As far as mercury in the sea goes, humans have little to do with it and geological processes a great deal. For example the Arbuckle Mountains were a high mountain range, that have been severely leveled as a result of millions of years of erosion. The Arbuckle Mountains were originally as tall as the Himalayas. At the time they formed, the Appalachians were much higher than they are today — more like the present-day Rocky Mountains. While the Atlantic Ocean was still in its infancy, the Appalachians were already being attacked by erosion. For the last 100 million years, erosion has carved away the mountains, leaving only their cores standing.

  54. Purely out of idle curiosity :

    Assuming we can trust the measurements at least, and argue about the rest of the paper later, doesn’t this imply that the CFC ban was a waste of time?

    Assuming that the Chlorine must be released from deposited salt. There can’t be many processes that deploy the energy needed to break the ionic bond in an NaCL molecule.Direct solar exposure or radiation absorption? Otherwise you’d have to look for a biochemical enzyme driven process surely?

  55. Dodgy Geezer says:
    January 15, 2014 at 4:18 am

    Er…. does this mean that we can have our cheap, safe CFCs back now…?

    Thought not….
    >>>>>>>>>>>>
    A patent is good for 17 years and can be renewed once so that is 34 years. The Montreal Protocol went into force on January 1st, 1989. 34 years later is 2023…..

    SEE: BUSINESS STRATEGY AND THE ENVIRONMENT, VOL. 6, 276±286 (1997)
    THERE’S MONEY IN THE AIR: THE CFC BAN AND DUPONT’S
    REGULATORY STRATEGY

  56. @- Gail Combs
    “Izen humans don’t MAKE elements unless you are talking nuclear reactions. Like every other living thing we concentrate the elements/ molecules that are useful to us. We are just a heck of a lot more inventive compared to fungi or termites.”

    Fair point, we extract and concentrate elements and molecules in far greater quantities and faster than natural processes.

    @-“As far as mercury in the sea goes, humans have little to do with it and geological processes a great deal. ”

    No, historical data on mercury levels preserved in human and animal hard tissues shows clearly that the natural background level was far below present levels until around the 1850s. Then industrial extraction massively increased the environmental levels with the elemental mercury we emit spreading worldwide, its conversion to soluble divalent mercury causes it to end up in the oceans where it is concentrated into the food chain. Pre-industrial samples do not show anything like the present day levels of mercury contaminattion of the seas or the food chain.

  57. @- Mike Ozanne
    Purely out of idle curiosity :
    Assuming we can trust the measurements at least, and argue about the rest of the paper later, doesn’t this imply that the CFC ban was a waste of time?

    No, this chlorine is too reactive and water soluble to make it to the stratosphere where ozone depletion takes place.
    NASA confirmed some time ago that the chlorine that depletes ozone in the stratosphere comes from human CFCs by direct sampling with an old U2 spy plane.
    And the isotope fingerprint proves it is anthropogenic.

  58. Joe Born says:,
    The top post says

    The study is the first time that molecular chlorine has been measured in the Arctic, and the first time that scientists have documented such high levels of molecular chlorine in the atmosphere.

    Aren’t orders of magnitude then irrelevant?

  59. Kent Jeffreys says:
    January 15, 2014 at 7:19 am

    I see from the photo at the press release that at least one of the instruments used by these researchers was attached directly to plywood. Any chance that part of their chlorine measurement resulted from emissions from the plywood?
    >>>>>>>>>>>>>
    Possibly. Polychlorinated dibenzo-p-dioxins and dibenzofurans in plywood combustion gas

    When you are talking a half part per million it does not take much to get contamination.
    Chlorine in breath condensate–a measure of airway affection in pollinosis?

    …Chlorine was measured by means of a sensitive coulometric technique and cys-LT by an EIA technique. Serum ECP was measured and lung function tests were performed and symptoms noted during both occasions.
    RESULTS:

    Significantly higher concentrations of chlorine in EBC [exhaled breath condensate] (p = 0.007) and ECP in serum (p = 0.003) were found during the pollen season compared to post-season. Chlorine levels tended to be higher in patients who reported of chest symptoms compared to those who denied symptoms during the pollen season (p = 0.06). Areas under the receiver-operated characteristic curves (AUC(ROC)) were compared and similar discriminative power to identify exacerbations of asthma was recorded by chlorine in EBC (range 0.67-0.78) and ECP in serum (range 0.64-0.78).
    CONCLUSION:

    It is concluded that chlorine in EBC and ECP in serum decreased significantly post-season, and this is suggested to mirror the decrement in airborne antigen. It is furthermore proposed that chlorine in EBC and ECP in serum tend to have a similar capacity to identify seasonal variations in airborne pollen in patients with asthma….

    I wonder if anyone handling the equipment had asthma or allergies….

  60. Mike Ozanne:

    At January 15, 2014 at 7:39 am you ask

    Purely out of idle curiosity :

    Assuming we can trust the measurements at least, and argue about the rest of the paper later, doesn’t this imply that the CFC ban was a waste of time?

    Assuming that the Chlorine must be released from deposited salt. There can’t be many processes that deploy the energy needed to break the ionic bond in an NaCL molecule.Direct solar exposure or radiation absorption? Otherwise you’d have to look for a biochemical enzyme driven process surely?

    The answer to your first question is, probably.

    Ferdinand Engelbeen gave an excellent answer to your second question(s) in his first post so I again link to it to save you needing to find it.

    http://wattsupwiththat.com/2014/01/15/high-levels-of-molecular-chlorine-found-in-arctic-atmosphere/#comment-1536483

    Richard

    PS You may not know that Ferdinand and I have been strong protagonists for many years so my evaluation of the high quality of his post is not biased.

  61. Back in the early days of handwringing about the ozone hole, there was an article in Science News about meythl chloride release from sea water as a potential source of stratosperic chlorine. I can’t find the article, but here are a few more complete references.

    http://www.inchem.org/documents/cicads/cicads/cicad28.htm#_28ci4000

    Natural sources of methyl chloride dominate over anthropogenic sources…
    Over the Pacific Ocean, the concentration of methyl chloride is higher in the lower troposphere than in the higher layers. However, over the continents, the concentration is independent of the altitude. Thus, the ocean seems to be a source of methyl chloride (Geckeler & Eberhardt, 1995). In the oceans, algae, especially planktonic algae, are considered to be responsible for most of the methyl chloride production. However, this has not been fully proven.

    http://www.ccpo.odu.edu/~lizsmith/SEES/ozone/class/Chap_10/10_4.htm

    4.2 Ocean Production of Methyl Chloride and Methyl Bromide

    Biological activity in the ocean processes some of the dissolved chlorine, bromine, and iodine salts. Seaweed produces methyl iodide (CH3I). Reactions in seawater replace the iodine with bromine to produce methyl bromide (CH3Br). Further reactions replace bromine with chlorine to produce methyl chloride (CH3Cl). A portion of each of these substances escapes to the atmosphere. CH3Br from the atmosphere may also dissolve in the ocean and be converted to CH3Cl. Methyl chloride has an atmospheric residence time of 1.5 years and is the most important natural source of chlorine for the stratosphere.

    http://www.ess.uci.edu/pub/714

    Title: Methyl chloride in a deep ice core from Siple Dome, Antarctica
    Abstract: Methyl chloride (CH3Cl) is a naturally occurring ozone-depleting substance and a significant component of the atmospheric chlorine burden. In this study CH3Cl was analyzed in air bubbles from the West Antarctic Siple Dome deep ice core with gas ages ranging from about 65 kyr BP to the Late Holocene. CH3Cl levels were below the modern Antarctic atmospheric level of 530 ppt in glacial ice ( 456 +/- 46 ppt, 33-65 kyr BP) and above it during the early Holocene (650-700 ppt, 10-11 kyr BP). For most of the Holocene, CH3Cl levels were 500-550 ppt, with good agreement between CH3Cl levels in this core and in the Dome Fuji ice core (Saito et al., 2007). Several late Holocene ice core samples (< 2 kyr BP), show evidence of enrichment in CH3Cl relative to South Pole ice core samples of overlapping gas age. The Siple Dome record suggests that CH3Cl levels in the glacial Southern Hemisphere atmosphere were about 16% lower than those during the mid-late Holocene. Citation: Saltzman, E. S., M. Aydin, M. B. Williams, K. R. Verhulst, and B. Gun ( 2009), Methyl chloride in a deep ice core from Siple Dome, Antarctica, Geophys. Res. Lett., 36, L03822, doi: 10.1029/2008GL036266.

    So, don't blame me for the chlorine in the atmosphere!

  62. Ferdinand Engelbeen says:
    January 15, 2014 at 2:10 am

    So, in my opinion, the origin of the free chlorine is largely known, and probably more from the increased metabolism via the methylchloride route than from the salt/HCl route…

    Also, from one of my refs in the post I just made (three URLs an into the moderation queue) is this confirmation:

    http://www.ccpo.odu.edu/~lizsmith/SEES/ozone/class/Chap_10/10_4.htm

    4.1 Sea Salt Production of Sodium Chloride (NaCl) and Hydrochoric Acid (HCl)

    The most common source of chlorine to the atmosphere is sea salt spray. Breaking waves and wind-blown foam spray millions of tiny particles and gases into the atmosphere. The tiny particles contain dissolved sodium chloride (NaCl or ordinary table salt). As the particles evaporate, both NaCl and hydrogen chloride (HCl) are released as a gas. Both of these molecules are highly soluble, and are removed by redissolving in the ocean or by dissolving in rainwater and being redeposited in the ocean or on land. Their atmospheric residence time is of the order of one week and they contribute negligible amounts of chlorine to the stratosphere.

    4.2 Ocean Production of Methyl Chloride and Methyl Bromide [I quoted this before]

    Biological activity in the ocean processes some of the dissolved chlorine, bromine, and iodine salts. Seaweed produces methyl iodide (CH3I). Reactions in seawater replace the iodine with bromine to produce methyl bromide (CH3Br). Further reactions replace bromine with chlorine to produce methyl chloride (CH3Cl). A portion of each of these substances escapes to the atmosphere. CH3Br from the atmosphere may also dissolve in the ocean and be converted to CH3Cl. Methyl chloride has an atmospheric residence time of 1.5 years and is the most important natural source of chlorine for the stratosphere.

  63. Izen,

    Since many readers here are unwilling to pay 35.95 to read Munthie et al, perhaps you can explain their basis for knowing the percentage of human contribution?

  64. Ferdinand Engelbeen,

    My guess is that the molecular chlorine comes from oxidation of NaCl to sodium peroxide plus molecular chlorine. This is energetically favorable because ozone is a much stronger oxidizing agent than is chlorine. Sodium peroxide formed this way would be expected to react quickly with water vapor in the air to yield NaOH. NaOH reacts quickly with CO2 to yield sodium carbonate, and then further with water and more CO2 to yield sodium bicarbonate. Of course, the detailed mechanism of the formation of chlorine might involve catalysis with some other species.

    The relative oxidation potentials are shown here http://www.ozoneapplications.com/info/oxidizing_potential_of_ozone.htm

    An old preparation method for sodium peroxide was reaction of solid sodium iodide with ozone, yielding molecular iodine (a palladium tube was used to speed the reaction via catalysis, mechanism unknown). Iodine is easier to reduce than chlorine, of course, but ozone is still a much stronger oxidizing agent than chlorine.

    The observation that the chlorine level correlates strongly with ozone and drops to near zero at night, combined with the requirement of a very strong oxidizing agent (sufficient to reduce Cl ion to Cl2) indicate a direct reaction of ozone with NaCl as most likely.

  65. Ferdinand Engelbeen: UV is not the only “light” that will disassociate NaCl in solution. Gamma and Xray also – All are omnipresent to a degree. GK

  66. Interesting that there is a diurnal cycle from 0-400 ppt. Does this not imply that Cl- ions can be released into the atmosphere from salt spray (from melting sea ice, wtf?) in sufficient quantities each day to reach the stratosphere in our polar deserts where there isn’t enough precipitation to wash it out of the air?

  67. Anthony Watts says:
    January 15, 2014 at 5:20 am

    Ferdinand, an excellent synopsis. May I suggest that you write a letter of rebuttal to Nature Geoscience on this? See: http://www.nature.com/ngeo/authors/index.html

    Thanks Anthony and others. I think we were -again- put on the wrong leg by some PR guy who wrote the press release. I haven’t baught the article (did give up that as what they ask for money is a shame, especially if one want to read a lot of related articles at once), and have no time to go to the university’s library in the next 1.5 week (visit to Valencia, Spain), But I may ask it Judith Curry, working in the same institute… Or if someone has access to Nature Geosciences articles…

    On the other hand, their supplementary information is free and excellent:

    http://www.nature.com/ngeo/journal/vaop/ncurrent/extref/ngeo2046-s1.pdf

    From chapter 4 in the SI:
    In summary, we found no clear relation between the age of the sea ice and chlorine levels. We also found no clear directional preference. High chlorine levels were found to correspond to long residence times in the boundary layer within 500 km of Barrow independent of wind direction.

    Thus independent of the origin of the air coming in over ice/open ocean/land (snow/vegetation)? There is no direct link I see with ice/snow melting and/or a larger open sea surface…

    Both HCl and Cl2 have short life times in the atmosphere (4 hours and 10 minutes resp.), thus are produced in situ from a precursor (which thus isn’t HCl itself), absorb on the snow surface and/or react with other species (organics, O3,…) in the atmosphere, aerosols and on the snow surface. The latter, solid surface reactions, are very complicated and hardly known in detail…

    They measured a lot of species, but I haven’t seen a direct link to CH3Cl (methylchloride) which can be the source of the continuous supply of chlorine/HCl precursors in the Arctic…

  68. citizenkla says:
    January 15, 2014 at 7:04 am

    Did you mean Chlorine – VCM – PVC? with a butadiene inhibitor for bulk shipment of the VCM?

    Indeed: at that time 325,000 tonnes per annum chlorine and 500,000 tonnes VCM, mostly used locally to produce PVC. Since my retirement they expanded the (membrane) chlorine factory to 500,000 tpa feeding a lot of other production units in the neighbourhood: MDI (for polyurethane), epoxy resin precursors, titanium dioxide (white dye for paints, inks,…)…
    MDI manufacturing sends HCl back that then is used again in the VCM oxychlorination process…

  69. Gail Combs says:
    January 15, 2014 at 8:05 am

    When you are talking a half part per million it does not take much to get contamination.
    Chlorine in breath condensate–a measure of airway affection in pollinosis?

    I was aware that the white blood cells attack invaders by surrounding them with NaOCl (bleach) and NOx, but I wasn’t aware that the sensitivity of the measurements was already so good that they could measure the increase of chlorine in the exhaled air… Very interesting information!
    But I suppose that the researchers were aware of that and stayed away from the direct intake…

  70. Steve Fitzpatrick says:
    January 15, 2014 at 8:28 am

    My guess is that the molecular chlorine comes from oxidation of NaCl to sodium peroxide plus molecular chlorine.

    It is one of the probable mechanisms (I suppose that you mean by O3 for the last part), but as the chlorine levels seems independent of the wind direction and the catch area is about 500 km according to their SI, there should be a drop if the wind direction is from the land side.

    Looks more like a continuous supply from another precursor…

  71. Izen says:

    “Pre-industrial samples do not show anything like the present day levels of mercury contaminattion of the seas or the food chain.”

    Mercury is being dumped in the oceans from leakge by the millions upon millions of consumer flourescent lights that were pushed by your enviro-cronies, Izen. Have you demanded that they must immediately stop producing those curly bulbs?

    Or, is it only bad when you can blame it on industry — the same industry that makes your life so much longer, healthier, and more wonderful than it would be without industry?

  72. …Huey said… The sea ice that lasts from one winter to the next winter is decreasing.

    Sea ice is decreasing? That’s news to me, and to a lot of readers here.

  73. ‘The level of molecular chlorine above Barrow was measured as high as 400 parts per trillion, which is a high concentration considering…’

    I now know the way to deal with the U.S. deficit. In April I will make a voluntary contribution; not of four hundred billion dollars, nor of a measly four hundred million, nor even four hundred thousand dollars; no; I will graciously give up a whole two months worth of breakfasts at McDonald’s and contribute a grand total of four hundred dollars – yep, four hundred dollars – for a massive pay down of one trillion dollars of the deficit. And, if just a handful of additional benefactors, each contribute $400.00, the U.S. deficit problem will be solved. And, if that $400.00 cuts into any of their car payments, heck, just give the bank 4 cents that month: they’ll be happy with it.

  74. Trygve Eklund says:
    January 15, 2014 at 1:48 am
    At that time, we were taught that free chlorine was generated by the action of UV light on sea water.

    As we know, sea water has a lot of NaCl in it. And due to the different attractions of Na and Cl for electrons, we have Na+ and Cl-. And it is certainly possible for UV light to knock the extra electron loose from Cl- to form a neutral Cl atom. Then two Cl atoms would combine to form a diatomic Cl2 molecule.
    The more sea water that is exposed to sunlight, the more Cl atoms could form. So in this way, if more polar ice melts, more sea water is exposed to the sun and more Cl2 could form. But this is an extremely convoluted way to combine melting polar sea ice with extra Cl2. It makes as much sense as trying to find the weight of a captain by weighing the ship with the captain on it and then weighing it again with the captain off it. The extra area of total ocean water exposed to UV light is an extremely small fraction.

  75. G. Karst says:
    January 15, 2014 at 8:30 am

    Ferdinand Engelbeen: UV is not the only “light” that will disassociate NaCl in solution. Gamma and Xray also – All are omnipresent to a degree. GK

    Agreed, but I suppose that most of the energy reaching the surface in the high energy band is UV…

  76. This was measured in 2009, sea ice was lower, including multi year ice.
    This is now 2014, sea ice is greater, especially including multi year ice.
    They are acting as if the sea ice was still diminishing, as before, when it is actually increasing/back to normal.
    They are essentially saying 2009 measurements are 2014 measurements and should be treated as such.
    They seem to not know or care what sea ice has been doing lately.
    They may not know because they know nothing outside their specialty, and/or they may not care because supporting “the cause” makes them feel good, not supporting it will get them fired, and supporting it supports the governments drive for total control and thus gets them grant money.

    Until I see present day measurements, this study is irrelevant.

  77. @Katherine

    Well said Katerine. At least you are thinking.

    >>The major source of elemental mercury in the Arctic regions is coal-burning plants around the world.

    >Yeah? How can they be so sure of that? What’s their basis for this claim? How about all the naturally burning coal seams?

    izen and his ilk are really wrong on this one. OMG this has to be repeated so many times….

    The main source of mercury in the atmosphere is the OCEANS because it is there where the stuff is available in huge quantities that utterly dwarf AG emissions. Upwelling waters bring masses of it and it emerges from the ocean and can be measured in the air just like anything else.

    There is an atmospheric monitoring station at Cape Point (y’all know where that is?) in South Africa which monitors the wind blowing from Antarctica. It has lots of mercury in it because the oceans between RSA and Antarctica pump it out just like everywhere else. If it was ‘down there’ in the deeps for 1500 years it may have an isotope different from some other, but I seriously doubt the claim that the isotope ratio has anything to do with coal burning. There is simply no easy way to nail that down. The whole environment has mercury in it and it forms part of the soil everywhere.

    What was VERY interesting about my visit to the Cape Point station is that is that the scientists there found, when they switched from daily to hourly measurements, that the mercury level in the atmosphere occasionally dropped to ZERO for several hours at a time. There has been no explanation of this phenomenon that contradicts all atmospheric circulation models that say mercury is well mixed and constant all over. But it clearly is not.

    The emergence of Cl from the ocean can easily explain this vanishing act and it is worth investigating it further.

    If there is an air monitoring station at Point Barrow, it should also be measuring airborne mercury and it should show, on an hourly basis, significant changes, maybe dropping if Cl goes up. It may be that the detection method does not differentiate between an Hg+Cl molecule of some sort and gaseous Hg on its own. Or maybe it does. Whatever the case, this is the first solid idea that I have seen since my visit that points in the general direction of a viable answer to the question, “What natural process is capable of stripping all the mercury out of the atmosphere as it passes over the ocean?” We know the process is natural because there is no ‘unnatural’ process going on between Cape Point and Antarctica, so the head honcho said. The monitoring station is a fine piece of work manned by volunteers from around the world.

  78. “How the sea salt is transformed into molecular chlorine is unknown.”

    S’obvious, innit. Global warming, any fool can see that.

    Nothing an extra few million dollars’ worth of research won’t get to the bottom of.

  79. Excellent review, Ferdinand Englebeen.
    I was surprised by the conclusion that molecular chlorine could be produced from brine (sea water) or sodium chloride (sea salt, anhydrous) and UV light. If so, someone would have long ago developed a solar chlor-alkalai process that is much more energy efficient than using electricity and probably much more profitable than simply evaporating sea water for sea salt. Also, having spent a couple decades in the frozen north and having used NaCl as an ice melter, I never noticed chlorine above the sidewalk and drive. Perhaps if these researchers had lived somewhere other than Atlanta, they wouldn’t have suggested this improbable mechanism for chlorine.

    And, if it is truly the first Arctic measurement of atmospheric molecular chlorine, I suppose it qualifies as “unprecedented.”

  80. Fascinating, Jim!

    Persistent Organic Pollutants (POPs) including chlorinated substances have long been measured the Arctic. This research may point to a new, natural mechanism for the formation of chlorinated substances. Of course, the Industrialized West has been blamed for this pollution and its health effects upon indigenous Arctic peoples:

    Persistent organic pollutants, or POPs for short, are highly toxic chemicals that travel long distances through air, water, and migratory animals; accumulate in terrestrial and aquatic ecosystems; and move up the food chain into the bodies of animals and people. They belong to a class of chemicals known as organochlorines (OCs), which are resistant to biodegradation and accumulate in the environment over long periods of time. They are known to cause endocrine, reproductive, and immune system disruption, neurobehavioral disorders, and cancers, including breast cancer.

    http://www.panap.net/issues/pesticides-health-and-environment/persistent-organic-pollutants-pops-and-indigenous-people-arctic

    Folks snickered when Pres. Reagan said that trees caused pollution, but years later, this was also proven. https://earthdata.nasa.gov/featured-stories/featured-research/volatile-trees

  81. “Ferdinand Engelbeen says: January 15, 2014 at 2:10 am…”

    Excellent synopsis Ferdinand!
    Even with your answer back to Anthony, I agree with Anthony’s request. Only I don’t think you need to file an official rebuttal, just the chemical synopsis and link to the 1998 paper.

    Darn good comments Lewis and Steve!

    I was chewing over how O₂; (ozone) managed to act like a battery in causing electrolysis of seawater to release free chlorine atoms. Bit Ferdinand’s synopsis is far more likely. Since ozone quickly reacts away, without UV to drive the ozone production the reaction would cease at night, all six months of it.

    Electrolysis of sea salt solution disassociates the salt. This is one way to produce sodium hypochlorite (bleach) as an end result (NaCl => Na+ ClO- +H₂O). A process used by backcountry people (hikers, campers, military) to sterilize their drinking water.

    I was also curious why the ‘researchers’ ,(cough cough) didn’t look for the normal ‘suspects’ when free chlorine is found, like all of the metals it is so delightfully reactive with; for that matter ozone is also quite happy to react with metals too.

    Add to that the idea that the ‘researchers’ also claim hypobromous acid is formed because of free chlorine and O2₂ floating around. Imagine that!

    I was under the impression that chlorine was more reactive than bromine and O₂ topped them both. Why blame chlorine?

    I also wondered why iodine wasn’t mentioned as it is certainly common in the sea.

    As for mercury, as Gail Combs mentioned, mercury and mercury compounds are common in many areas of Earth’s crust. Some areas even have elemental mercury pooling freely until it gets exposed to air. An odd note is that many of the ‘recent’ papers claiming to prove oceanic mercury levels (methylmercury) are human caused, are mostly based on ‘models’… Sound familiar?

    Izen is spreading p’izen knowledge huh? Well, weeds and trolls hate to keep their waste of space and filth all to themselves.

  82. “Ferdinand Engelbeen says: January 15, 2014 at 9:30 am

    G. Karst says: January 15, 2014 at 8:30 am

    Ferdinand Engelbeen: UV is not the only “light” that will disassociate NaCl in solution. Gamma and Xray also – All are omnipresent to a degree. GK

    Agreed, but I suppose that most of the energy reaching the surface in the high energy band is UV…”

    Don’t forget that earth’s magnetosphere causes high energy particles to enter at the magnet pole; some of these are seen as the aurora borealis.

  83. I wonder if the chlorine molecules go away in the Arctic spring night (average low in March in barrow -28.4°C) because chlorine is a liquid below -34°C? Did the researchers measure the temperature whilst sampling?

  84. Well, with the help of Judith Curry, I received the full article directly from Dr. Huey…

    In the article there is not the slightest hint of melting ice or local/global warming in the Arctic. So far for the discrepancy with the press release…

    There is more than enough seasalt in the snowpack over the Arctic ocean and land (as measured during the campaign) that may be the source of chlorine detected. The main cause in this case being the oxydation of chloride to chlorine by ozone and light: there is no detectable free chlorine if the ozone concentration is too low and the chlorine levels drop to zero at night. Chlorine levels also drop somewhat around midday, as the more intense sunlight dissociates Cl2 into Cl radicals which are very reactive and react near immediately with organics and other halogen inorganics (bromides, iodides and derivatives). This was measured as an increased level of organic and inorganic peroxy radicals.

    Further, the high chlorine levels were detected near ground up to a few meters, which points to a ground source, which may be salt spray on snow or ice, seems like more solid surface chemistry.
    Similar releases of bromine and iodine were detected in the past, but this is the first time for chlorine.
    Last but not least, the authors warn:
    “high levels of Cl2 observed at Barrow do not imply high levels of Cl2 in the entire Arctic.”

    My impression is that the research was set up profesionally and well done, but no conclusion can be derived from a single measurement series on a single place over a short period of time…

    Anyway the hints on melting ice in the press release and the interview with Dr. Huey have not the slightest base in the research itself, but may have helped its publication… And if the salt spray at the snow/ice surface is the main source, less ice would give less chlorine, not more?

  85. Billy Liar says:
    January 15, 2014 at 1:58 pm

    I wonder if the chlorine molecules go away in the Arctic spring night (average low in March in barrow -28.4°C) because chlorine is a liquid below -34°C? Did the researchers measure the temperature whilst sampling?

    Not a chance: water is a liquid below 100°C, but that doesn’t say that all water drops out of the atmosphere below that temeperature. It is a matter of vapour pressure for water, CO2 and chlorine alike. Because of the very low concentrations no liquid chlorine will form, but around -80°C, some strange chemicals (chlorine nitrate) are formed on the surface of the ice crystals of stratospheric clouds. That reacts with HCl to form chlorine, which reduces ozone in spring…

  86. richardscourtney says: @ January 15, 2014 at 8:10 am

    You may not know that Ferdinand and I have been strong protagonists for many years so my evaluation of the high quality of his post is not biased.
    >>>>>>>>>
    I will second that. Ferdinand’s comment was very well done.

  87. RichardsCourtney … what makes you feel you can verbally abuse people at will on this site? I guess your Christian name was given for good reason!

  88. So there is salt trapped in the ice, and the salt evaporates and dissociates into chlorine, which kills the ozone over the arctic. Izzere an arctic ozone hole ?? I always thought the ice was fresh water. I believe the segregation coefficient says the salt prefers the liquid phase (of water) to the solid phase, so it gets expelled back into the ocean, as the seawater freezes. The CO2 in the arctic ocean also gets expelled from the ice, when the water freezes (same reason), and that results in the ocean water adjacent to the ice being super-saturated with CO2, so the ocean water then expels the excess to the atmosphere; which is why the atmospheric CO2 over the arctic has a p-p cycle of 18-20 ppm over the seasons, compared to 6 ppm at Mauna Loa.

    Yeah I know there are brine pockets in the ice; but that has to be peanuts of salt, compared to what is expelled to the water on freezing; and it would be hard to convince me, that on melting of that ice, that brine gets exposed to the atmosphere preferentially, rather than just slipping into the warm ocean that is causing the ice melt anyway.

  89. izen says:
    January 15, 2014 at 3:25 am

    “Given that at least half of the background mercury levels we measure are human made, that is that anthropogenic sources have doubled the natural background level, {Munthe et al 2001} at least half the mercury measured anywhere must be from human activity releasing it from natural sequestration.”

    Yeah, especially these Chinese curly light bulbs for saving the environment. I think we will be seeing a big spike in Hg over the next decade or so.

    Re molecular chlorine in the arctic, getting the source of the chlorine wrong, it would be another level of abstraction for these guys to expect the solar wind’s ionized particles that give rise to the aurora as good candidates for splitting off Cl from NaCl which is abundantly in the air or, more likely, Ferdinand’s HCl.

    Interestingly, a way to recover spent HCl (conversion to salts) in industrial processes is to react the resulting salts with sulphuric acid:
    e.g.
    2NaCl + H2SO4 => 2HCl + Na2SO4.

    Sulphates are abundant in the atmosphere and the sea, too! Hey, how about protons from the solar wind (which are H^+) + sulphates in the atmosphere from volcanism and blown/evaporated seawater chlorides giving us HCl. The sun may have more than one way to effect climate!

  90. Wherever this chlorine comes from, it’s still a WW1 poison gas.

    So I’m pleased to be able to say we’re still doomed.

  91. This recently published article may be relevant:

    Production of gas phase NO2 and halogens from the photolysis of thin water films containing nitrate, chloride and bromide ions at room temperature
    Nicole K. Richards-Henderson,a Karen M. Callahan,a Paul Nissenson,b Noriko Nishino,a Douglas J. Tobias*a and Barbara J. Finlayson-Pitts*a
    Phys. Chem. Chem. Phys., 2013,15, 17636-17646

    UV light generating molecular chlorine and NO2. Pay-walled, so I can’t read the details; I don’t know for sure if the reaction was done in the presence of air or not… but I assume it was..

  92. This Russian group shows that the reaction is ozone with sodium chloride to form hypochlorite ion:

    Kinetics and Catalysis
    August 2010, Volume 51, Issue 4, pp 492-496
    Mechanism and kinetics of the reaction of ozone with sodium chloride in aqueous solutions
    S. D. Razumovskii, M. L. Konstantinova, T. V. Grinevich, G. V. Korovina, V. Ya. Zaitsev

    Sodium hypochlorite could react with H+ (probably from CO2 + H2O –> H+ + HCO3- ) to form Cl2 plus sodium bicarbonate. So the reaction may take place in the relatively concentrated saline solution that forms when sea ice forms, and the initial product is hypochlorite from ozone reacting with HCl. Makes sense: only during daytime (ozone), only near the surface, and only where ice forms from seawater, generating a residual salt solution of relatively high concentration on the ice surface.

  93. All those studies over the last couple decades on fluorine from Freon, and they never once checked for chlorine?

    We have a pretty obvious problem with our research data gathering agenda.

  94. “On Lonely Mission, Robot Starts Descent Into Volcano”. This article appeared in the NYT on 16th Jan 1993 and referred to NASA’s Dante robot mission into Mount Erebus in the Antarctic. The purpose was to examine gaseous emissions from the volcano, expected to contain significant volumes of Chlorine. The robot failed after a short run due to a break in the optical fibre link. It was withdrawn and never heard from again?
    There was some UK TV programme based on this Expedition, but I am unable to locate it so far.

    How about volcanic emissions as the source of whatever form of Chlorine has been detected?

  95. Caleb says:
    January 15, 2014 at 3:05 am
    Can chlorine oxidize? Or does oxidization have to involve oxygen?

    Yes, chlorine is an oxidising agent, where oxidation is defined in terms of gaining or losing electrons. Here, the reactant which gains electrons is the oxidizing agent, while the reactant which has lost electrons has been oxidized. Molecular chlorine gains two electrons to end up as two chloride ions.

  96. stevefitzpatrick says:
    January 15, 2014 at 6:06 pm

    This Russian group shows that the reaction is ozone with sodium chloride to form hypochlorite ion:

    That may nail it down: it may be a reaction of ozone with salt spray on ice and snow (thin film reaction) and/or at the surface of brine ponds leftover from the freezing ice.

    But it doesn’t explain that the chlorine levels are independent of wind direction: Salt spray is limited in level and extent farther away from the oceans, although most of the chlorine seems to be formed in the direct neighbourhood.

    At the other side, methyl chloride (chloromethane) is relative abundant in the lower troposphere, and especially over the oceans, where a lot is formed by algue:

    http://www.inchem.org/documents/cicads/cicads/cicad28.htm#_28ci4000

    The concentration reaches 1.2 µg/m3 (0.6 ppb) in ambient air, compared to an average surface snow chloride of 6.6 ppmv, but methyl chloride is continuously replenished from the oceans (and land sources), locally or from other places on earth.
    From the above reference:
    The tropospheric reactive chlorine burden of approximately 8.3 × 106 tonnes chlorine is dominated by methyl chloride (~45%) and trichloroethane (~25%).
    The reaction mechanism is not given, but probably also by ozone/high energy light. The original referenced abstract is here:

    http://onlinelibrary.wiley.com/doi/10.1029/94GB03103/abstract

    According to the research at Barrow, there is no correlation with (salt) aerosols, which can be a fast source. Thus the real origin of the local high chlorine levels still is unknown. It is a pity that the researchers didn’t measure local methyl chloride levels…

  97. I’m pressed for time, and could only scan about 50% of the discussion thread to this point, but it seems there is no WUWT consensus on the source of the chlorine (jape intended).

    I propose the following:

    Seawater gets carried up into the atmosphere as liquid aerosols, and the water evaporates into vapor, leaving microscopic crystals of NaCl as a solid aerosol, which can migrate into the upper levels of the atmosphere. There, full strength UV will split atomic chlorine from the sodium. The chlorine will then recombine into molecular chlorine and, upon further interaction with UV, split again, recombine again, etc.

    Nice hypothesis. Any reason to believe it? There is an atmospheric layer of ionized sodium at high altitude. This is used for “guidestar” laser probes, which sample the optical properties of the atmosphere in order to adjust modern telescopes equipped with adaptive optics. They project a laser beam on a line parallel to the optical axis of the telescope and measure the optical distortion of the light scattered or re-radiated by the sodium layer.

    I simply ask: Whence came the sodium layer?

    It makes the perfect counterpart to: Whence came the chlorine?

  98. izen says:
    January 15, 2014 at 7:59 am

    No, historical data on mercury levels preserved in human and animal hard tissues shows clearly that the natural background level was far below present levels until around the 1850s. Then industrial extraction massively increased the environmental levels with the elemental mercury we emit spreading worldwide, its conversion to soluble divalent mercury causes it to end up in the oceans where it is concentrated into the food chain. Pre-industrial samples do not show anything like the present day levels of mercury contaminattion of the seas or the food chain.

    —————–
    I’d like to see a citation on this claim. Here’s one citation that gives a counter argument:

    http://www.ncbi.nlm.nih.gov/pubmed/5060046

    Science. 1972 Mar 10;175(4026):1121-2.
    Mercury concentrations in museum specimens of tuna and swordfish.
    Miller GE, Grant PM, Kishore R, Steinkruger FJ, Rowland FS, Guinn VP.
    Abstract

    The mercury levels of museum specimens of seven tuna caught 62 to 93 years ago and a swordfish caught 25 years ago have been determined by instrumental neutron activation analysis. These levels are in the same range as those found in specimens caught recently.

    ————

    The mercury in tuna scare began in the late 1960s due to Japanese industrial pollutants in tuna and other locally caught fish causing massive health problems in some Japanese locations. This study (of which one author was Frank Rowland, of Rowland and Molina fame – i.e. the guys who linked ozone depletion with Freon) found no difference in mercury levels between recently caught fish and museum samples dating back to a century earlier. The samples were all from the high seas. Obviously, mercury concentrations in farmed fish in Japanese inshore waters would be much higher. Japan has an intensive fish farming culture that dates back to the 1930s, by the way.

  99. In my time of military duty in the 70’s and 80’s we learned that to survive in the arctic you should look for old sea ice because it would have less salt in it and i am not a chemist but that tells me that salt can be coming out of the ice by other means.

Comments are closed.