'Superglue' for the atmosphere

From Goethe University Frankfurt A research group lead by scientists at the Goethe University Frankfurt discover details on how clouds form

This news release is available in German.

It has been known for several years that sulfuric acid contributes to the formation of tiny aerosol particles, which play an important role in the formation of clouds. The new study by Kürten et al. shows that dimethylamine can tremendously enhance new particle formation. The formation of neutral (i.e. uncharged) nucleating clusters of sulfuric acid and dimethylamine was observed for the first time.

Previously, it was only possible to detect neutral clusters containing up to two sulfuric acid molecules. However, in the present study molecular clusters containing up to 14 sulfuric acid and 16 dimethylamine molecules were detected and their growth by attachment of individual molecules was observed in real-time starting from just one molecule. Moreover, these measurements were made at concentrations of sulfuric acid and dimethylamine corresponding to atmospheric levels (less than 1 molecule of sulfuric acid per 1 x 1013 molecules of air).

The capability of sulfuric acid molecules together with water and ammonia to form clusters and particles has been recognized for several years. However, clusters which form in this manner can vaporize under the conditions which exist in the atmosphere. In contrast, the system of sulfuric acid and dimethylamine forms particles much more efficiently because even the smallest clusters are essentially stable against evaporation. In this respect dimethylamine can act as “superglue” because when interacting with sulfuric acid every collision between a cluster and a sulfuric acid molecule bonds them together irreversibly. Sulphuric acid as well as amines in the present day atmosphere have mainly anthropogenic sources. Sulphuric acid is derived mainly from the oxidation of sulphur dioxide while amines stem, for example, from animal husbandry. The method used to measure the neutral clusters utilizes a combination of a mass spectrometer and a chemical ionization source, which was developed by the University of Frankfurt and the University of Helsinki. The measurements were made by an international collaboration at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research).

The results allow for very detailed insight into a chemical system which could be relevant for atmospheric particle formation. Aerosol particles influence the Earth’s climate through cloud formation: Clouds can only form if so-called cloud condensation nuclei (CCN) are present, which act as seeds for condensing water molecules. Globally about half the CCN originate from a secondary process which involves the formation of small clusters and particles in the very first step followed by growth to sizes of at least 50 nanometers. The observed process of particle formation from sulfuric acid and dimethylamine could also be relevant for the formation of CCN. A high concentration of CCN generally leads to the formation of clouds with a high concentration of small droplets; whereas fewer CCN lead to clouds with few large droplets. Earth’s radiation budget, climate as well as precipitation patterns can be influenced in this manner. The deployed method will also open a new window for future measurements of particle formation in other chemical systems.

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79 thoughts on “'Superglue' for the atmosphere

  1. Assuming I even came close to reading that correctly, is it possible that the key to succesfully ‘seeding’ clouds for rain, was just discovered in our own pollution?

    • +1
      Yes – prior to the industrial revolution, the world was in drought… until all that rain from our seeds caused the clouds to dry up…. now drought is caused by global warming. You see it’s simple. Man is evil…

  2. Sooo, more sulphur dioxide from burning coal and more amines from growing animals for meat (mostly) leads to more cloud formation which leads to lower global temperatures? What a greenmare!

    • This is exactly correct! Throw in even more ammonia from landfills, PLUS ice-forming bacteria (per Jasper Kirkby of CERN, who wrote me the following:

      There is a lot of current interest in the ice-forming properties of bacteria and spores that are found in clouds. Ice is important since most of precipitation from clouds is initiated by ice via the Bergeron-Findeisen process. Ice-forming nuclei are rare in the atmosphere so there is a large amount of supercooled liquid water in clouds. Biological material seems to be among the most efficient ice nuclei known and can lead to rapid rainout of a supercooled cloud, hence their importance.
      Best regards, Jasper

      I’d say that the science of this stuff is far from settled.

  3. This article sounds like it might lead to the first effective cloud-seeding. That would be great news!

    • I can see the librules are getting excited about this. A new tax based on how much rain you get since other areas might not get as much from the Climate Rain Budget.

    • I recall a paper which attributed the great warmth of the mid-Cretaceous to the oceans being too hot to produce enough biological CCNs to seed clouds. Naturally, it was not popular among CACA spewers.
      http://www.jameslovelock.org/page35.html
      Abstract: The major source of cloud-condensation nuclei (CCN) over the oceans appears to he dimethylsulphide, which is produced by planktonic algae in sea water and oxidizes in the atmosphere to form a sulphate aerosol. Because the reflectance (albedo) of clouds (and thus the Earth’s radiation budget) is sensitive to CCN density, biological regulation of the climate is possible through the effects of temperature and sunlight on phytoplankton population and dimethylsulphide production. To counteract the warming due to doubling of atmospheric CO2, an approximate doubling of CCN would he needed.

      • http://www.ncbi.nlm.nih.gov/pubmed/18403703
        Science. 2008 Apr 11;320(5873):195. doi: 10.1126/science.1153883.
        Amplification of Cretaceous warmth by biological cloud feedbacks.
        Kump LR1, Pollard D.
        Author information
        Abstract
        The extreme warmth of particular intervals of geologic history cannot be simulated with climate models, which are constrained by the geologic proxy record to relatively modest increases in atmospheric carbon dioxide levels. Recent recognition that biological productivity controls the abundance of cloud condensation nuclei (CCN) in the unpolluted atmosphere provides a solution to this problem. Our climate simulations show that reduced biological productivity (low CCN abundance) provides a substantial amplification of CO2-induced warming by reducing cloud lifetimes and reflectivity. If the stress of elevated temperatures did indeed suppress marine and terrestrial ecosystems during these times, this long-standing climate enigma may be solved.

      • mpainter October 9, 2014 at 2:25 pm

        My skepticism meter just got stuck on max.

        I think the expression you’re looking for is: “My bullshit meter just pinned.”
        The movement of the needle in an analog gauge is constrained by two pins positioned at the extreme left and right limits of motion. At ‘rest’ the needle abuts the left pin, at ‘max’ the needle abuts the right pin. Engineers refer to the needle hitting the max limit as ‘pinning’.

      • The paper I linked is from when Lovelock still ascribed to extreme CACA. Its hard to find papers that don’t genuflect toward CACA, so the trick is to find what’s valuable in them.
        I cited Lovelock’s paper on biological CCNs because that part of it is valid. There are of course other sources of CCNs over tropical oceans than biological, but the sulphate aerosols from phytoplankton are important, so at least a partial answer to F. H. Haynie’s question.

    • “If the stress of elevated temperatures did indeed suppress marine and terrestrial ecosystems during these times, this long-standing climate enigma may be solved.”
      The paleonological record certainly does not support the idea that Cretaceous low-latitude ecosystems were “suppressed”.

  4. I’m assuming that the higher concentration of sulphur dioxide in modern times might not have a strong effect on monsoon rains (or the formation of clouds with smaller droplets elsewhere negates any positive effects) but I have some doubts that the effect of the higher concentration in modern times is large because the “Learning from the Monsoon” post that shows the NW Indian Monsoon rain fall has a trend of 0.08mm/decade over a century and a half which is not greater in the past two decades. I know that the effect on the albedo of the Earth will be much greater than on monsoon rainfall but it is strange.

  5. “Sulphuric acid as well as amines in the present day atmosphere have mainly anthropogenic sources.”
    Somehow I doubt that statement regarding sulphur. Clouds and rain have been happening since the first volcanoes spewed sulphur compounds into the ancient atmosphere.

    • Good point. However, Mann-made modeling can accommodate any theoretical assumption to meet their goal. I am sure, much like oceans suddenly becoming heat sinks, the mechanism magically occurred recently so anything in the real world or before ______(insert date) was done not because of sulfur.

    • And as for dimethylamines being due to animal husbandry, as far as I know there were a lot of large animals around before agriculture, almost certainly more than now as a matter of fact,

      • True, but these animals did not poop into confined animal feedlot operations (CAFOs), which concentrate the manure and enhance ammonia and hydrogen sulfide formation through ponding of wastes. CAFO lagoons are immense bioreactors that spew all sorts of cloud-forming pollution into the atmosphere:

        CAFOs for dairy cattle, swine, poultry and other food animals hold thousands of large animals or hundreds of thousands of smaller animals.
        Most of the regulatory focus has been on CAFOs’ water pollution. But the CAFOs’ barns, feedlots and manure storage areas also foul the air with ammonia, hydrogen sulfide, particulate matter, volatile organic compounds and other contaminants.
        Animal waste accounts for about half of total natural and man-made ammonia in the United States, according to a 2003 National Research Council report. Those emissions are associated with health effects that range from throat irritation to major cardiovascular diseases and increased rates of morbidity. Many are also precursors to other air quality problems, such as smog and acid rain.

        http://www.eenews.net/stories/1060001938

      • DMA formed in the oceans from animal life, e.g., fish wastes, partitions into the gas phase since ocean pH is basic.

  6. This is a huge development. Kulmala has led the effort to understand atmospheric nucleation bursts, which occur over wide (1000-km on a side) areas fairly often (every few days in some places). There has been a question whether these particles will grow to CCN size (50 nm) before they evaporate. Svensmark and the CLOUD experiments attempted to show that ions might allow the particles to grow to CCN size, but the experiments were not fully successful. Now these folks are showing that ions are NOT needed (they modified the CLOUD chamber to strip out all cosmic rays during the experiments.) Just a neutral combination of sulfuric acid and diethylamine can lead to stable clusters that can then grow without much evaporation. If this neutral growth mechanism contributes substantially to cloud growth, it would suggest that the cosmic ray effect on ion formation would not necessarily be an important route to cloud formation.
    Full article and Supporting Information available here:
    http://www.pnas.org/content/early/2014/10/02/1404853111.full.pdf+html?with-ds=yes

  7. Plainly, “The Science is Settled” – something others may believe – but I think there are some unknown unknowns out there.
    Yeah – I am a bum boatie doofus.
    But – see the top article.
    Were you aware of this?
    Were you???
    Auto

  8. You gotta love the ever increasing definition of anthropogenic emissions. When the paper says
    ” Sulphuric acid is derived mainly from the oxidation of sulphur dioxide while amines stem, for example, from animal husbandry.”
    What they mean is dimethylamines and trimethylamines are produced by rotting cattle manure. Yes folks it really is bullshit.
    Keith

  9. So that helps to explain the hiatus in global temperature ie removal of sulphur from fuel over the last 15 years would have had a warming effect to counterbalance the natural cooling cycle and hence global temperatures are flat. Which would also mean that the introduction of fuels with sulphur would have had a cooling effect 100 years ago and hence they should adjust up old temperature records. But they would never do that.

    • I have been thinking for a long time that the modest temperature rise at the end of the last century was very likely caused, not by pollution, but by removal of pollution during the 60’s through the 90’s start ing with London’s clean air acts following it’s ‘killer smogs’ occurring in the 50’s. This certainly lends support to that possibility.
      If that is the case, this (AGW) must go down in the Guinness Book of Records as the biggest human mistake since we got down from the trees…

    • And also
      … acid and dimethylamine corresponding to atmospheric levels (less than 1 molecule of sulfuric acid per 1 x 1013 molecules of air).
      Perhaps that was meant to be 1 x 10^13 molecules.

    • My question if all the Sulphuric acid is from anthropogenic sources how did it rain before we produce all that Sulphuric acid?

  10. This topic should have been funded decades ago, especially given IPCC’s statements about cloud uncertainty.
    Am I right in thinking that this opens the possibility of a method of harmless, or even beneficial (more rain where it’s wanted, less where it isn’t), geo-engineering?

    • Am I right in thinking that this opens the possibility of a method of harmless, or even beneficial (more rain where it’s wanted, less where it isn’t), geo-engineering?
      Pandora’s Box being opened here. As soon as you “make it rain” somewhere that otherwise would not have gotten rained on, somewhere else where the the rain would have landed later doesn’t get rained on. Might be a good thing if you’re diverting the moisture from somewhere that was getting too much, but you could be diverting it from somewhere that otherwise would have gotten just he right amount… Not to mention that countries could wage war by “stealing” the rain from countries they are upwind of. Or get the timing right and flood them…. And of course there’s the whole issue of weather forecasts only being good for a few days out, so who the heck knows what effect seeding a few clouds now has on weather 6 months out….
      Every time I hear the word “geo-engineering” I shudder.

      • That’s why there are international treaties for irrigation. The US now sometimes lets enough of the Colorado River reach Mexico to keep the practically extinct anadromous fish of the Sea of Cortez from going totally extinct. For decades all the river’s flow was used to irrigate the US Southwest and more recently to keep its burgeoning human population watered.

      • “Might be a good thing if you’re diverting the moisture from somewhere that was getting too much, but you could be diverting it from somewhere that otherwise would have gotten just he right amount…”
        Wouldn’t it be better for California to steal a little rain while it’s in a drought from states downwind, even if they suffer a little? It is in a desperate situation, those downwind are not.
        “who the heck knows what effect seeding a few clouds now has on weather 6 months out….”
        Probably nothing catastrophic. Anyway, if it does have nasty effects, it can be stopped. This form of geo-engineering is reversible.
        “Every time I hear the word “geo-engineering” I shudder.”
        Well, the genie seems to be out of the bottle, so the negative effects of one country, say Pakistan, stealing water from India aren’t something that can be easily stopped. I shudder more at the word “mitigation.” If it’s a choice between the two, geo-engineering of global cloudiness is the winner.

      • Most rain that falls, evaporates from the immediate vicinity where it fell. ‘Stealing rain’ also implies ‘giving it back to fall again’.

      • Existing large scale irrigation schemes already move rain from where it fell to be evaporated off elsewhere, but it probably sorts itself out fairly quickly. The evaporation from an area devastated by floods soon moves on to be distributed in some sort of order courtesy of the global circulation.
        What comes around goes around.

  11. Does water vapor need a condensation nuclei to condense? Or does the presence of CCN increase the rate of condensation (and lower the height)?
    For some reason I had naively thought that water automatically condensed out as the air cooled. It seems to me that CCN’s would clear out the water vapor quicker and cause climate heating rather than cooling.

    • Normally, yes, for a droplet to form, water vapor needs a tiny particle (solid or liquid cloud condensation nucleus) upon which to condense, ie change state from gas to liquid.
      Water vapor can however be supercooled well below freezing for several hours to form droplets without CCN, as in cloud chambers for detecting subatomic particles. Alternately, droplets can form above freezing if the air is supersaturated to about 400%.

      • Water condenses at about 135% RH when there are no condensation nuclei.
        Liquid water freezes at -35°C when there are no nuclei.
        Assuming 60%RH at 80.0°F (26.7°C), RH equals 100% at 64.9°F (18.3°C) and 135% at 56.4°F (13.6°C).
        Assuming a 9.6K/km lapse rate, those are 0.9 km and 1.3 km above the ground respectively (incorrectly assuming constant pressure).

      • milodonharlani and Robert
        Could you direct me to a source of education explaining in depth with regards to the condensation and freezing of water vapor as you have discussed above. I think I need to know more about this.

      • I must admit that my thoughts were such as Genghis above. I’m burning “google” but haven’t found the depth of knowledge that I’m looking for. This is one of those “need to know” moments. Why is nucleation required and when/why /what are the parameters where nucleation is not required.

      • Eyesonyu & Genghis:
        To be sure, everything connected with climate is fraught with difficulty. But the behavior of water vapor is pretty straight forward, if complicated because of the strangeness of H2O.
        Under “normal” conditions, the formation of liquid water droplets from water vapor in the air does need CCNs, as I noted. Robert Clemenzi provides more detailed info on how gaseous H2O behaves in the absence of solid or liquid CCNs than I provided.
        Suffice it to say that the temperature or humidity (saturation) requirements for condensation in the absence of CCNs are rarely encountered in a state of nature on this our home planet.
        I hope this helps, but fear it doesn’t.

      • milodonharlani
        Thanks for the reply. I’m burning google to the point of a google mentdown. It has become an interesting journey but not the answers I’m looking for.

  12. Just walking around, one does not get the impression that cloud formation is a big deal. Get some convection started and there they are. But not without those amines and sulfates, I guess.

  13. You know, I thought they were about to describe my finding of observations over 50 years of clouds from aircraft (mainly in mining exploration aircraft but also commercial airline flights). I have looked at structures 10s of km long – long straight “grooves” like a fault in rock, compressed boxy structures, the mares tails and mackerel scales, folds in clouds etc. and came to the conclusion that clouds must posses a mechanical adhesion or attraction between groups and masses of droplets that resists, to a remarkable degree, shear forces caused by winds. The analogy between clouds and geological structure in rock formations, after years doing photgeological interpretation, field mapping and the like naturally would give significance to such observations by a geologist.
    But no, the Planck phalanx missed the forest for the trees in aiming there spears at human caused pollution and missed out on a geologist’s understanding of structure in large masses and tabular formations.

    • More: I thought there must be Van der Waals molecular attraction giving the clouds plastic behavior. I’m content to go with crazy glue.

  14. While we are at it, I wonder what the relative contributions of cow dung and forest sources of amines are?
    http://www.nitrogen2011.org/_poster_presentations/S2_Kieloaho.pdf
    “Samples were collected from a Scots pine forest at SMEAR II station at Hyytiälä, southern Finland..”
    and: http://en.ilmatieteenlaitos.fi/science-news-archive/-/asset_publisher/5UiQ/content/the-alkylamine-concentrations-in-urban-air-are-lower-than-those-in-forest-air?redirect=http%3A%2F%2Fen.ilmatieteenlaitos.fi%2Fscience-news-archive%3Fp_p_id%3D101_INSTANCE_5UiQ%26p_p_lifecycle%3D0%26p_p_state%3Dnormal%26p_p_mode%3Dview%26p_p_col_id%3Dcolumn-2%26p_p_col_count%3D1
    “The alkylamine concentrations in urban air are lower than those in forest air”
    Manmade REDUCTIONS in Amines, doncha know!!

    • Yes, there is a lot of organics in the air in pine forests, not to mention eucalypt forests. Reminds me that many years ago when I was working on organic aerosol emissions from airline operations I was told (in confidence) by a man from the Swedish EPA that they had been planning to set a maximum permissible level for any and all organic aerosols, without specifying composition. However they had to give up the idea since it would have made coniferous forests (which cover 50% of Sweden) illegal.

  15. The perfect set up for continued climate panic and taxation. If it cools it’s our fault. It it warms it’s our fault. Bad humans.

  16. A really interesting article! Atmospheric repair is an important part of reversing climate change damage. Look forward to seeing what happens with this in the future! 🙂

  17. Back in the ’60s, an organic substitute for silver iodide was discovered, a bit by serendipity. Much like the sulphur, it formed the nuclei upon which water vapour could coalesce, forming raindrops into what was, a moment ago, a clear blue sky. I think it was called, Carnauba.

  18. Hmm, more cattle… less droughts?
    Makes sense. This certainly compliments Dr. Allan Savory’s finding that what we really need is MORE cattle, more grazing animals, a lot more of cattle to prevent the growth and creation of new deserts or help heal existing ones on the edges.
    [ http://www.ted.com/talks/allan_savory_how_to_green_the_world_s_deserts_and_reverse_climate_change.html ]
    So now even the Vegans have their hand in helping to destroy the world as we have known it.

  19. So more ccn more rain means less water in the atmosphere does that cause heating or cooling. Or is just more clouds and not necessarily more rain?

    • My hope is that it will mean more cloudiness (stopping further global warming) and more rain (because not all clouds will rain out). We won’t know until we try.

    • Less water vapor in the atmosphere means that the atmosphere has a lower enthalpy. Therefore, all those non-engineers who continue to assess the amount of heat in the atmosphere by measuring temperature can become over excited about how temperatures are rising. However, the amount of heat in the atmosphere may have stayed the same or even dropped due to the lowered enthalpy.
      (This is why water vapor cannot be directly compared to CO2 as a so called ‘green house gas’)

  20. “Sie haben herausgefunden, dass Amine möglicherweise…..” translates to:
    They found out, that amines possibly…..
    This is where I normally stop reading. Did they find out something or is it possible? But for sure, they need more money to find out.

  21. In short: The mechanism of the system of sulfuric acid and dimethylamine as CNN has been studied in the lab. Nothing is said about the concentration and the distribution of these molecules in the atmosphere. In addition, one has to compare it with the concentration of other CNNs.

  22. You ever been to San Francisco, or Humboldt county, or a paper mill. That smell in the air, the cabbage fart smell is dimethyl sulfide, or DMS.
    You can smell it long before you get there. It’s overpowering. It saturates your clothes, your pores, every fiber of your being. Stay long enough you can almost forget it’s there. But every morning you wake up, there it is again, strong as ever.
    I guess people on the East Coast could kid themselves into thinking that smell is due to power plant fumes or car exhaust. We on the West Coast, the honest ones anyway, with our onshore flow can’t pretend it comes from any place but the ocean.

    • According to the USEPA, that pleasant smell in New York City is body odor, dirty diapers etc.! EPA says that these are a measurable and significant source of ammonia emitted into the atmosphere.

      Note: “Domestic” includes human perspiration/respiration, infant diapers, cigarette smoke, domestic fertilizer use, and household ammonia use (these estimates along with the landfill estimates are not currently in the NEI and were added to develop the figure).

      http://www.epa.gov/ttnchie1/eiip/techreport/volume03/eiip_areasourcesnh3.pdf

  23. Well water doesn’t need fuming H2SO4 to make droplets. Any speck of dust, or a microbe, or a charged particle can do it. You just need some surface, that is not hydrophobic. The moisture in my car at night condenses on the windows, or mirror, but It never just falls out of the air in my car, as rain.
    I read a paper about some water studies back East, where they had figured out how to capture a single rain drop; any rain drop, and immediately isolate it, so they could analyze it. In this one study, every rain drop, already had a microbe colony in it. The droplet had apparently grown on one microbe, and while falling to earth the microbe had multiplied.
    Water is a polar molecule, and evidently likes sticking head first to surfaces; which I think means Oxygen end down.
    It’s that pesky 104.x degree angle in the bent water molecule, that makes all life possible.

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