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- Date: Mon, 21 Dec 1992 14:56:42 -0700
- Reply-To: PARSON_R@CUBLDR.COLORADO.EDU
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- From: PARSON_R@CUBLDR.COLORADO.EDU
- Subject: Re: ozone layerSEND/EDIT
- Lines: 141
-
- First of all I would like to thank Jeremy Whitlock for pointing out the
- statement in Van Nostrand's Scientific Encyclopedia (1989 edition, article on
- volcanoes) that Mt. St. Augustine put 289 billion kg (289 Mt) into the
- stratosphere. I've seen this impossible figure (it's hundreds of times larger
- than the total amount of HCl _in_ the stratosphere!) quoted in several places
- (Dixy Lee Ray's book, for example) but always without citation.
-
- This appears to be a horrible mistake on the part of the compilers of the
- encyclopedia. The article gives an accurate summary of Johnston's
- claim ("Volcanic Contribution of Chlorine to the Stratosphere: More Significant
- to Ozone that Previously Estimated?", _Science_ _209_, 491, 1980) that
- St. Augustine put *0.082-0.175* Mt of chlorine into the stratosphere (17-36%
- of the 1975 world production of chlorine in fluorocarbons). As I said in
- my previous post, these numbers are now considered to be too large. (In any
- case, they are at most _comparable_ with CFC emissions, not far in excess of
- them.)
- In the next paragraph, however, the encyclopedia states the impossible
- figure given above, apparently without seeing any discrepancy! I looked up
- Johnston's paper again and found the following (p. 492):
-
- "eruption of the Bishop Tuff from Long Valley Caldera, 700,000 years ago,
- generated 100 km^3 of air fall ash. If the magma degassed 0.25% chlorine
- (equivalent to Augustine Volcano), this eruption may have injected 289x10^9
- kg of HCl into the stratosphere..."
-
- Yup, there it is - it's for the Long Valley Caldera, _not_ for St. Augustine!
- This was one of the so-called "giant caldera eruptions" that occur every
- 100,000 years or so. These are unimaginably violent events, probably the
- most destructive weapons in Nature's arsenal (excepting asteroid collisions).
- For example, the most recent such eruption, Lake Toba in Indonesia (~70,000
- years ago) dumped ash on India and Madagascar and may have triggered an ice
- age. Another example is Yellowstone Park, which blows out every 600,000 years
- or so (numbers from memory). If Long Valley were to erupt today it would kill
- millions. 289 Mt HCl is quite conceivable for such an event (I have seen
- similar estimates for Toba).
-
- Conceivably, a typesetter accidentally substituted Augustine for Long Valley;
- it's still an inexcusable mistake on the part of the Encyclopedia.
-
- More recently Jeremy Whitlock wrote:
-
- >I disagree that the baseline is as important as the relative change. It
- >may be a fact of nature that the ozone layer is thinner over the antarctic,
- >and indeed polar plantlife is adapted to a higher UV-B flux. The relative
- >change, which is what will affect lifeforms, is on the same order as
- >relative changes with latitude and season elsewhere on the globe.
-
- Records going back to 1956 show a thick ozone layer over the antarctic
- (although the seasonal variation is somewhat different from that in the arctic
- - the winter low of ~275 persisted until November, because of the polar
- vortex. The ozone hole consists of a _decrease_ from this naturally low
- springtime baseline). UV-B levels in polar regions are always very low,
- because the sun is never high and light takes a long path through the
- atmosphere. For this reason, the ozone hole is _not_ directly dangerous to
- humans or other species that have evolved closer to the equator. There were
- reports last year of blind sheep, etc. in Chile and Patagonia, but it is very
- unlikely that this was due to the ozone hole, since these same sheep do just
- fine in the Andean highlands where they get much more UV-B.
- The real danger is to organisms that have evolved in the normally low
- UV-B, such as marine phytoplankton. These get exposed to springtime UV-B
- levels that approach, and on occasion exceed, those characteristic of an
- Antarctic midsummer (Frederick and Alberts, _Geophys. Res. Lett._ _18_, 1869,
- 1991.) In other words, summer has suddenly become twice as long, as far as
- UV-V goes. The effect is exacerbated because the antarctic sea ice is much
- more transparent in spring than in summer. There is one recent study (_Smith
- et al., _Science_ _255_, 952, 1992) which finds ~10% reduction in
- "phytoplankton productivity" upon passing into the hole - this is well within
- natural year-to-year fluctuations (~25%) but could be serious if it represents
- a cumulative effect. I will let the regular subscribers to this list discuss
- the significance of this sort of effect since my knowledge of biology (let
- alone ecology) is minimal.
-
- >This tells me that ClO and ozone concentrations are anticorrelated. I'd
- >still like to know if cause-and-effect has been demonstrated for man-made
- >sources.
-
- I addressed this in an earlier post, which appears not to have gotten out
- (Jan Schloerer tells me he didn't see it). The observation of anticorrelation,
- together with laboratory experiments that reproduce it, is convincing evidence
- that the ozone hole is due to Cl (and Br) catalyzed reactions. It remains to
- show that the chlorine is manmade. The evidence for this consists of
- measurements of sources and sinks, a laborious task that has been going on
- for ~20 years. The concentrations of the various source gases have been
- measured _as a function of altitude_, and this provides us with a way to
- estimate the flux of these gases into the stratosphere.
-
- The total amount of chlorine in the stratosphere has increased by a factor
- of 4 since ~1950 (S. Solomon, _Nature_ _347_, 347, 1990). The major natural
- source is CH3Cl; concentrations of CH3Cl in the troposphere have fluctuated
- but have not shown any steady increase over this period. As discussed
- previously, volanoes don't add up to enough - and in any case the frequency
- of stratosphere-piercing eruptions (about 1 per year, most of which only
- go a little way into the strat) has not increased. CFC emissions _did_
- increase over this period, in about the right amounts.
- To pin things down a little more firmly, consider the altitude dependence
- of the CFC concentrations. These are typically constant all the way through
- the troposphere (showing that there is no chemical sink for them in the
- troposphere, just as the popular discussions say) and then drop off rapidly
- starting at about 15 km, where there begins to be enough UV-C around to
- break them up. For example, the concentration of CFCl3 in 1980-1983 was
- measured at 0.2 parts per billion from 0-14 km, drops to 0.1 ppb by 20km,
- and is down to 0.02 ppb at 25 km. (For comparison, total stratospheric
- chlorine was about 2.0 ppb in 1980, and remember that each CFCl3 gives
- 3 Cl atoms, so that 0.1 ppb CFCl3 destroyed between 14 and 20km gives
- 0.3 ppb Cl, a sizable fraction of the total amount that had been accumulating
- over 30 years - and that's just _one_ CFC (the second most widely-produced
- one). The calculation is a good deal more complicated than this (the CFC's
- don't decay all at once, UV-C pops off one Cl and the others come off
- after subsequent reactions which can take years at the low concentrations
- in the strat., - and all the time stuff is drifting up and down, north and
- south) but that's the basic idea.
-
- Ref. for the CFCl3 data: R. P. Wayne, _Chemistry of Atmospheres_, 2nd
- edition, Oxford, 1991, p. 162 - I'm sorry I don't have a _Science_ or
- _Nature_ reference, but this book is pretty readable.)
-
- Additional evidence:
-
- 1. _Fluorine_ concentrations in the strat. have also been rising - the
- concentration of HF (the final destination for F in the strat) has increased
- by a factor of 10 since 1978 (Zander et al., _J. Geophys. Res._ _95_,
- 20519, 1990.)
-
- 2. Some of the decay products of CFC's (radicals like CF2O, formed when
- the CF2Cl radical reacts with oxygen) have also been observed.
-
-
- One final remark: it is important to distinguish between _ozone depletion_,
- which so far is a small effect (5% for the US over the past decade, more
- in southern Australia, much less (essentially none) in the tropics), from
- the Antarctic ozone hole, which is a huge, but so far localized, effect.
- Although there is a strong case linking CFC emissions to the Antarctic hole
- (and to the much smaller springtime "dimple" over the north pole), there is
- still argument about the causes of the depletion at mid-latitudes - there is
- a substantial majority view, but I would not call it a consensus. As an
- outsider, though, I reason as follows: ClO wipes out 3% of the world's
- ozone every spring. Most of it comes back, but we see a small decrease -
- ~3% _per decade_ - over the earth as a whole. Seems reasonable that effect #2
- is linked to effect #1, although this is not proof.
-
- Robert
-