Guest essay by Michael Wallace, Hydrologist
The prevailing model of seasonal and long term global ozone depletion is grounded in a principal assertion that emissions of industrial refrigerants and propellants (also known as Ozone Destroying Substances, ODSs) are the primary causal agents.
I review that assertion from a perspective relating to my ongoing research of the global geostrophic circulation regime and its associated moisture. I often write that motions of mass and energy within the planet’s hydrosphere are routinely captured by geostrophic integration of kinetic and enthalpic signatures. The enthalpic signatures are known to scale according to routinely identified categories of temperature, vapor pressure, and the total air pressure of any parcel of the atmosphere. This holds in particular for the full atmospheric integration of the troposphere with the stratosphere and the mesosphere, up to an average altitude of 100 km above mean sea level (AMSL).
Vertical and horizontal profiles of the energy and momentum of these parcels with respect to any conceivable orientation can be examined for practically any time span. I’ve developed some profiles along these lines from easily available ERAI source material [1]. I have focused on parameters such as the “Evaporation minus Precipitation for the Full Atmosphere”, EP (mm/day), at posts such as this example on Geostrophic Waves.
Geostrophic maps of EP patterns are often interesting. In addition to Atmospheric Moisture Waves (AMW)s, they often align with easterly equatorial streamlines and sometimes with gyres. The equally important Geopotential Height Z (kg/m) contours don’t clearly express such waves, but are also interesting if only because they often align with the westerly streamlines of the middle latitudes and sometimes with gyres as well.
I compared some full atmosphere ozone (O3) maps to equivalent months, from ERAI for EP and Z as shown in Figure1 a and b. Much might be said of the resulting comparison, including that the patterns sometimes align with EP and /or Z patterns and sometimes align with gyres. The January plot of Figure 1b, with the associated ozone hole lobe in blue branching northeast from the Philipines, and the associated gyre shown by the streamlines of the adjacent plots, seems particularly compelling.
Those figures obviously suggest that ozone can correlate inversely with atmospheric moisture. From my perspective, it appears that the major gyres, such as the Equatorial Northern Hemisphere Pacific Gyre continually replenish their long lived atmospheric parcels with moisture as they rotate through the wet Equatorial Trough that encircles the planet along the equator. That might account for continual destruction of O3 via Reaction 1, leading to the blue contour bands in the central images column of that figure set.
Figure 1. 1.a. Comparison of three full atmosphere parameters for December 1982 and
1.b. January 1983. Sources [1], [2].
These apparent connections are supported by empirical industrial knowledge. Ozone is prized for its remarkable properties at purifying water when dissolved in it. Naturally ozone must first be synthesized before it is added to the water. Yet many water treatment textbooks and other resources can be found to detail the problems of industrial production of ozone in the presence of trace water. Such knowledge includes evidence that Ozone will readily react with water and itself be destroyed, sometimes according to the simple equation labeled below as REACTION 1.
H30 + O3 + EUV → OH + H20 + O2 (REACTION 1.)
Where:
H30 is the hydronium ion, whose concentration defines pH
O3 is ozone
EUV is the UV energy source that drives the reaction
OH is the hydroxide radical
H20 + O2 are water and oxygen respectively.
It follows that an increase in atmospheric moisture, such as a rise in vapor pressure of water, or relative humidity, might be expected to lead to a decrease in ozone concentration (which is equivalent to its partial pressure). This notion appears to be verified from randomly selected vertical profiles of concurrent measurements from sources for the following Figure 2 a and b.
Figure 2 2a. Vertical profile of RH and Ozone for 20 September 2011 over Boulder, CO 2b. Vertical profile of RH and Ozone for 3 April, 2012 over Boulder, CO. Source [3].
Confirmation of high and inverse correlations between water vapor and ozone therefore emerges from both lateral and vertical comparisons, including from exploration of individual research airplane flights that concurrently monitored O3 and H2O with altitude, as shown in Figure 2.
Figure 1 demonstrates that many aspects of these patterns appear to be captured by barotropic weighted environments. A quasigeostrophic (QG) conceptual model of ozone distribution therefore seems justified. For a QG model to be tested, the parameter that is measured must be integrated across the full atmosphere thickness, but allowed to vary laterally. Although Figure 1 is a good example of that, I’ve found that the NOAA resource for Figure 2 also contains some time series of ozone and moisture for the full atmosphere. From their data I’ve produced Figure 3, to cover the full time series of the moisture as a limiting case. The actual ozone record for this location goes even further back in time. Given the high correlations shown, it likely offers potential for reconstruction of the past moisture patterns in my view. This is yet another purely scientific reason that I find ozone so interesting.
Figure 3. Time series of ozone and water vapor for full atmosphere thickness over Boulder Colorado. Source listed in subtitle within image. Source [3].
In any case, once again this alternate conceptual model of water vapor concentrations inversely driving ozone concentration is demonstrated. As noted, the latest confirmation shown of three independent comparisons is from a full atmosphere thickness parcel series over several decades of measurements.
Profoundly drier statements about water vapor can be found, if water is even mentioned at all, in many comprehensive ozone reports including relatively recent publications by the World Meteorological Organization (WMO) (2014, 2005)[4,5]. In the most recent of those summary reports, the primary causal constituents cited for ozone destruction in the atmosphere remain chloroflourocarbons (CFCs) and Halons. Although rarely some low key sources will partially acknowledge the potential for ozone destruction by water vapor [6], the role of atmospheric moisture is typically carefully constrained [7] and segregated to a limited domain of intermittent high Antarctic stratospheric clouds that are asserted to incubate ODSs every Antarctic winter[4].
This Antarctic winter incubation and the subsequent Antarctic Spring release of ODSs over that continent, are key foundations of the entire ozone destruction argument. Readers are encouraged to explore those assertions deeply, where they will find that the very winds themselves are argued to be caused by this ODS incubation phenomenon. I could cite many for this strange assertion but for now I quote from the 2014 WMO report [4] which states on page 4.1 that “Stratospheric temperature changes due to Antarctic ozone depletion are very likely the dominant driver of the observed changes in Southern Hemisphere tropospheric circulation in summer over recent decades, with associated surface climate and ocean impacts.”
I’ve engaged in limited explorations of that prevailing Antarctic ODS incubation model, simply to confirm or falsify the associated claim that the peak in polar ozone depletion for the Southern Hemisphere is in its (austral) Spring and that the peak for polar ozone depletion in the Northern Hemisphere occurs in its (boreal) Spring. The WMO resource and others sources appear to be careful to leave a reader with this perception even as low key qualifying statements accompany that assertion.
Plots I’ve derived from the ozone researchers’ data such as this sample series Animation 1., and the plates of Figure 4., appear to falsify that claim. In other words as the images show, the ozone depletion doesn’t oscillate from one pole to another each year. Rather both hemispheres exhibit largely synchronous ozone trends. That’s quite interesting one might think. How many other aspects of the two poles oscillate in synchrony? I can only think of one myself, namely polar auroras.
Animation 1. Arctic Ozone Climatology
A generally accepted notion of ozone genesis, circulation, and extinction comes in part from studies of the Brewer – Dobson circulation [8] and of the well known vertical temperature lapse rate inflection at the tropopause. In this conception, UV forcings cause ozone to emerge into the middle stratosphere at its highest concentration levels, and to diffuse to a minimum at the tropopause[9]. Meanwhile tropospheric air parcels rich in water vapor, which cross the tropopause, are thermally altered by the loss (condensation) of that vapor.
I only bring this up to somewhat round out the limited treatment of ozone I cover in this post. I could use this as a segue to the implausible arguments found in [4] and others that a primary source of water vapor in the stratosphere is from oxidation of anthropogenic methane! How the researchers determined that only water vapor from such a singular source could violate the thermodynamic constraints of our stratosphere remains a mystery, perhaps to be explored in a future post.
I’m primarily interested in the tropopause because it may be a significant factor in the EP surfaces I’ve profiled in the past. Also I happen to wonder if the cause of the temperature inversion at the tropopause might also be related to the significant releases of latent heat which accompany the universal condensation of water vapor at that altitude.
It may be, given the correlations shown, that at some times, some aspects of ozone data will resemble the remarkable atmospheric wave approach. This remains to be seen. If this is true, and given the primary content of this post, then many aspects of the current narrative of ozone circulation and destroying might merit some reevaluation. In particular, I’m interested to know if ozone pattern analysis can improve hydrologic forecasting.
Others may be more interested in how the CFC-Halon ODS model has remained at the forefront of all scientific and media publications (see for example [10] and [11]) concerning ozone in our atmosphere, given what is clear now about moisture as the principal ODS. I hope many will consider requesting answers to such questions from any and all who work on ozone research or who impact ozone mitigation policy and funding.
As I said, from my limited perspective, I’d like to reconcile residence times that are published concerning atmospheric circulation. For example, CFC and Halon ODS values are listed in the WMO 2014 resource with typically long atmospheric lifetimes. These lifetimes, reaching close to 600 years in extreme cases, appear to be based on the same crude 1D eddy diffusion model from the 1974 Nobel Prize winning literature source for modern ozone science [12]. Without any disrespect intended, such a model appears to be extraordinarily deficient in addressing the rich patterns of atmospheric circulation that actually prevail across our planet.
Accordingly I believe that the addition of geostrophic circulation mapping to such models offers promise towards more rational residence time estimates. Currently it is known that gyres encompass the longest residence times of any subregion across the planetary atmosphere. Residence times of 600 years would be unusual however.
Could there be some greater consistency of estimates of residence times in the future? I think so, but this advancement would require a more candid and greater mindfulness of the fundamental roles in time, space, and in the chemistry of atmospheric moisture relating to ozone destruction. In approaching that reasonable goal, it would hopefully produce the added benefit of weaning researchers away from the myraid unproven, implausible, and expensive notions now associated with CFC and Halon based ODS models.
Michael’s blog is at http://www.abeqas.com
Figure 4. Ozone in this northern hemisphere location consistently reaches its lowest levels towards the boreal autumn (September and October) Adapted from source [2]
REFERENCES
[1] http://www.cgd.ucar.edu/cas/catalog/newbudgets/index.html#ERBEFs downloaded file named ‘ERAI.EP.1979-2014.nc ‘
[2] acdisc.gesdisc.eosdis.nasa.gov
[3] National Oceanic and Atmospheric Administration, United States Dept. of Commerce, Earth System Research Laboratory, Global Monitoring Division, Ozone and Water Vapor Research Group
[4] World Meteorological Organization (WMO), Scientific Assessment of Ozone Depletion: 2014, World Meteorological Organization, Global Ozone Research and Monitoring Project—Report No. 55, 416 pp., Geneva,Switzerland, 2014.
[5] WMO Global Ozone Research and Monitoring Project Report No. 49 An Overview of the 2005 Antarctic Ozone Hole Prepared by Geir O. Braathen WMO TD No. 1312 WORLD METEOROLOGICAL ORGANIZATION
[6] https://www.giss.nasa.gov/research/briefs/shindell_05/
[7] https://www.nasa.gov/centers/langley/news/factsheets/HALOE-Ozone.html
[8] Salby, M.L. and P.F. Callaghan, 2005, “Interaction between the Brewer-Dobson Circulation and the Hadley Circulation. Journal of Climate 18 (20)
[9] Sivakumar, V., Bencherif, H., Begue, N., and Thompson, A.M., 2011, “Tropopause Characteristics and Variability from 11 yr of SHADOZ Observations in the Southern Tropics and Subtropics” Journal of Applied Meteorology and Climatology 50, pp. 1403-1416
[10]http://www.bendbulletin.com/sciencetech/5409884-151/a-chemical-could-delay-ozone-healing. This contemporary article appears to support my current representations on CFC causation assertions.
[12] Molina, M.J. ,and F.S. Rowland, 1974, “Stratospheric sink for chlorofluoromethanes : chlorine atomc-atalyzed destruction of ozone”. Nature Vol 249 June 28, 1974
Mike, the current theory states that ice crystals provide a surface for the reaction to occur. I see nothing to stop a mechanism in which water droplets can act similarly by dissolving the reactants. The reactions here are fairly well established ozone is used to purify water. can you distinguish from ozone depletion where ice forms or where water forms? If you go into reactions with water vapour you will need to get to grips with free radial reaction kinetics.
Gerontius it looks to me as if no ice is required, but that in the presence of ice the destruction of ozone may be possible at least as long as some vapor phase remains. The ozone theorists only point to ice as an incubator for chlorine and other halides. For what it is worth, I feel that my main contribution is not in the simple chemistry that I’ve dug up, but that the ozone and water vapor distributions are inversely related whether one looks at a full atmosphere or a layer within the atmosphere. The connections are sustained whether one looks vertically or areally. The connections persist whether one looks at a day or at decades. Moreover, I’ve drawn attention to the ozone catastrophe industry’s longstanding assertions of those high ice clouds that act as some sort of ozone killing incubator awaiting spring thaws. For that assertion to “hold water”, that episode must occur at each pole at that pole’s respective spring. This is a critical leg of their assertions. Yet that is not the pattern shown by the data. I also note they tread lightly around that part of the claim because the data doesn’t support it.. and yet, they decline to make this easy for everyone to see. I am a student and continue to learn and welcome that, But after decades of fear mongering and millions if not billions of dollars spent towards the ozone fear, I feel that the ozone research community needs to get to grips with the high inverse correlations to water vapor and the poor match of their noctilucent ice incubation theory to reality. They need to acknowledge those and more and deal with the fallout transparently and candidly.
Perhaps water vapor explains the relationship between the ENSO and ozone variance heretofore mysterious?
That sounds intriguing. I hadn’t heard of that.
Mike, it’s in the stratospheric ozone class lecture materials at Old Dominion U’s CCPO site. I tried upthread to post the link but the spam filter got it twice. I’ll try again in a separate comment following.
Mike, see my link above in this comment:
https://wattsupwiththat.com/2017/12/23/the-profound-and-dominant-impact-of-atmospheric-water-vapor-upon-ozone-destruction/comment-page-1/#comment-2700782
Look at chapter 2, section 4.2.4 and 4.2.5. we might have a correlation here.
Ozone has an interesting property rarely discussed. It is diamagnetic, or essentially repelled by magnetic fields, whereas oxygen is paramagnetic-attracted to magnetic fields.
The “returning” magnetic field of the earth is focussed on the polar regions.
What impact may this have on ozone regionality?
bubbagyro this is very interesting. I don’t know the answer, but I have noticed that ozone patterns around Antarctica often resemble aurora patterns around the same location. Coupled with the circulation aspects, I wouldn’t be surprised to learn that moisture, ozone, and auroras have some deeper connections, perhaps related to the diamagnetic feature you brought up.
Mike, have you looked for possible relationship between ocean surface pollution and droplet formation? I have a vague memory of a problem with small droplets growing big enough to fall out: if droplets are not raining out then presumably the RH goes up. The oceans are certainly polluted enough for some effect to be happening. Wolf number change IIRC.
I’ll spare you my guess that polluted ocean surfaces are a contributor to warming.
JF
Hi Julian, I have looked into that a little bit. I often get detoured in moisture investigations by the well known principal of cloud condensation nucleii. I also have put some time in to study literature on upwelling of marine aerosols. In fact, my first notion on those was that they might be supplying the major supply of the chlorine that catalyzes ozone destruction. The ozone research community exclusively attributes such chlorine to CFCs and disregards marine aerosols. Yet the mass of marine aerosols and the associated chlorides from the sea salts, that are lifted into the atmosphere, dwarfs the mass of CFCs. However more recently as this post shows, I’ve come to realize that moisture in and of itself can do all or most of the heavy lifting in ozone destruction.
I’m wandering around the answer to your question, but there is a lot still unknown, I think when it comes to condensation of droplets from water vapor. Your “vague memory” is essentially correct though.. for any given dewpoint temperature, as the RH reaches 100%, condensation of droplets occurs. The less known part in my view is the notion that aerosols or other tiny particles, including pollutants, are an essential ingredient for moisture condensation for the “nucleation” of the raindrop. I’m still learning myself and note that water vapor can definitely condense to a liquid or to a solid without any need for nucleation around a foreign particle. It only takes somewhat colder temperatures to happen.
Much more could be written and has been by many others of course. Perhaps if researchers can come to terms with the moisture – ozone correlations I’ve profiled here, they can advance some of these other questions in a more productive way.
Pop, many thanks. I took a short look but I’m mainly going by your excerpt. I study the SOI for my own moisture forecasting research. It certainly is within the ENSO compedium of indexes and in fact covers the “SO” in ENSO. It’s historically grounded in the concept of those pressure differences between Tahiti and Darwin. However what I have found most useful is that the Tahiti portion directly underlies a limb (I would call it) of the so called Atmospheric Wet Pool (AWP) (Zhang and Chen 2008). The AWP constitutes the greatest concentration of atmospheric moisture on the planet. The high atmospheric moisture limb of the AWP is known as the Southern Pacific Convergence Zone (SPCZ) (Kiladis et al., 1989). That limb passes over Tahiti.
So I think you have pointed to another area that could support this moisture ozone connection and it’s interesting and helpful that prior researchers have studied it, even if they were more focused on pressure correlation than moisture (and the two can be closely related in any case). I somewhat feel at this point that the negative correlation between ozone and moisture can be found wherever one might look, so long as care is taken to ensure that the same atmospheric parcels are examined. But this one is particularly interesting to me at least because of the association with the globally high moisture mass. Over time, I’ll try to examine that more closely myself. The mixed message of negative and positive correlations in the excerpt you provided will require careful attention to exactly what regions are evaluated. Or I (or anyone else with the interest of course) could just focus on the SPCZ itself and bypass the traditional SOI.
Thanks again, and I hope to keep in touch.
Kiladis, G.N., H. von Storch, and H. van Loon, 1989. Origin of the South Pacific Convergence
Zone. Journal of Climate 2(10), 1185-1189.
Zhang, C. and Chen, G. 2008. The atmospheric wet pool: Definition and comparison with the
oceanic warm pool. Chinese Journal of Oceanology and Limnology, 26, 440–449.
I’m just beginning my self-education on this subject so I sure appreciate the references, Mike. I will be cramming on this for a while but I’ll watch for your next article. This is the best place I know to stimulate my mind in retirement.
Thanks! There will be plenty to keep you occupied.. 😀
This is all unnecessarily complex: ozone is naturally unstable. It has a half life, which, at the polar winter temperatures is about 3 months. This is the cause of the ‘ozone hole’