ozone facts

7/26/2019 Ozone Facts

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The amount of ozone in the atmosphere in any given volume is the summation of:1. (+) photoproduction of oxygen into ozone.2. (+) photoactivation and decay of N2! into N2 and ozone.". (#) destruction of ozone $ith time.%. (#) increase in rate of destruction &y increasing temperature.

'. (#) destruction of ozone &y $ater vapor.. (#) destruction of ozone &y other compounds catalysts.*. (+#) diffusion of ozone into or out of the volume &eing considered.

Table 1. Potential Effects of UV-B Increases.

EffectsState of

Knowledge

PotentialGlobalImpact

Plant Life Low High

Aquatic Life Low High

Skin Cance!odeate

to High!odeate

ImmuneS"stem

Low High

Cataacts !odeate Low

ClimateImpacts#

!odeate !odeate

$opospheic%&one

!odeate Low##

Ozone depletion

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0mage of the largest ntarctic ozone hole ever recorded (eptem&er 233).

Ozone depletiondescri&es t$o distinct &ut related o&servations: a slo$ steadydecline of a&out % percent per decade in the total volume ofozonein4arth5s

stratosphere(the ozone layer) since the late 16*3s and a much larger &ut seasonaldecrease in stratospheric ozone over 4arth5s polar regions during the same period. Thelatter phenomenon is commonly referred to as the ozone hole. 0n addition to this $ell#-no$n stratospheric ozone depletion there are also tropospheric ozone depletionevents $hich occur near the surface in polar regions during spring.

The detailed mechanism &y $hich the polar ozone holes form is different from thatfor the mid#latitude thinning &ut the most important process in &oth trends is catalyticdestruction of ozone &y atomic chlorine and &romine.718The main source of thesehalogenatoms in the stratosphere isphotodissociationof chlorofluorocar&on(99)compounds commonly called freonsand of&romofluorocar&oncompounds -no$nas halons. These compounds are transported into the stratosphere after &eing emittedat the surface.728oth ozone depletion mechanisms strengthened as emissions of 99sand halons increased.

99s and other contri&utory su&stances are commonly referred to as ozone-depletingsubstances(ODS). ince the ozone layer prevents most harmful ;


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2.1.1 99s in the atmosphereo 2.2


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photodissociateafter a&sor&ing an ultravioletphoton $hose $avelength is shorterthan 2%3 nm. This produces t$o oxygen atoms. The atomic oxygen then com&ines$ith 2to create ". zone molecules a&sor& ;< light &et$een "13 and 233 nmfollo$ing $hich ozone splits into a molecule of 2and an oxygen atom. The oxygenatom then >oins up $ith an oxygen molecule to regenerate ozone. This is a continuing

process $hich terminates $hen an oxygen atom Grecom&inesG $ith an ozonemolecule to ma-e t$o 2molecules: + "H 2 2

Ilo&al monthly average total ozone amount.
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http://en.wikipedia.org/wiki/File:Atmosphere_layers-en.svg


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Jayers of the atmosphere (not to scale)

The overall amount of ozone in the stratosphere is determined &y a &alance &et$eenphotochemical production and recom&ination.

zone can &e destroyed &y a num&er of free radicalcatalysts the most important of$hich are the hydroxyl radical(CK) the nitric oxideradical (NK) atomic chlorine(9lK) and&romine(rK). ll of these have &oth natural and manmade sourcesL at the

present time most of the CK and NK in the stratosphere is of natural origin &uthuman activity has dramatically increased the levels of chlorine and &romine. Theseelements are found in certain sta&le organic compounds especiallychlorofluorocar&ons(99s) $hich may find their $ay to the stratosphere$ithout

&eing destroyed in the troposphere due to their lo$ reactivity. nce in thestratosphere the 9l and r atoms are li&erated from the parent compounds &y theaction of ultraviolet light e.g. (5h5 is @lanc-5s constant 5M5 isfreAuencyof

electromagnetic radiation)

99l"+ hM H 99l2+ 9l

The 9l and r atoms can then destroy ozone molecules through a variety of catalyticcycles. 0n the simplest example of such a cycle7%8a chlorine atom reacts $ith an ozonemolecule ta-ing an oxygen atom $ith it (forming 9l) and leaving a normal oxygenmolecule. The chlorine monoxide (i.e. the 9l) can react $ith a second molecule ofozone (i.e. ") to yield another chlorine atom and t$o molecules of oxygen. Thechemical shorthand for these gas#phase reactions is:

9l + "H 9l + 2

9l + "H 9l + 2 2

The overall effect is a decrease in the amount of ozone. ?ore complicatedmechanisms have &een discovered that lead to ozone destruction in the lo$erstratosphere as $ell.

single chlorine atom $ould -eep on destroying ozone (thus a catalyst) for up to t$oyears (the time scale for transport &ac- do$n to the troposphere) $ere it not for

reactions that remove them from this cycle &y forming reservoir species such ashydrogen chloride(C9l) and chlorine nitrate(9lN2).

n a per atom &asis &romine is even more efficient than chlorine at destroying ozone&ut there is much less &romine in the atmosphere at present. s a result &oth chlorineand &romine contri&ute significantly to the overall ozone depletion. Ja&oratorystudies have sho$n that fluorine and iodine atoms participate in analogous catalyticcycles. Co$ever in the 4arth5s stratosphere fluorine atoms react rapidly $ith $aterand methane to form strongly &ound C$hile organic molecules $hich containiodine react so rapidly in the lo$er atmosphere that they do not reach the stratospherein significant Auantities. urthermore a single chlorine atom is a&le to react $ith

133333 ozone molecules. This fact plus the amount of chlorine released into the
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atmosphere &y chlorofluorocar&ons (99s) yearly demonstrates ho$ dangerous 99sare to the environment.7'8

[edit] Quantitative understanding of the chemical ozone loss process

0n 233* research on the &rea-do$n of a -ey molecule in these ozone#depletingchemicals dichlorine peroxide(9l22) also -no$n as the 9l dimer called intoAuestion the completeness of present atmospheric models of polar ozone depletion.The 9l dimer serves as a reservoir for chlorine in the atmosphere. s long as thechlorine is tied up in the dimer it is not availa&le for catalytic destruction of the ozone.@hotolysis of the dimer produces t$o 9l molecules $hich can participate in catalyticdestruction of ozone. 9hlorine Nitrate (9lN2) is another important reservoirmolecule.

9hemists at N5s /et @ropulsion Ja&oratory in @asadena 9alifornia remeasuredthe a&sorption cross#section for the 9l dimer $hich they reported to &e an order ofmagnitude lo$er than previously thought in the region &et$een "33 and "'3 nm.787*87E8

This lo$er a&sorption coefficient $ould imply that much less chlorine is availa&le forcatalytic destruction of ozone in the stratosphere as more of it $ould remain tied upin the 9l dimer.

That result motivated further measurements &y different methods resulting in cross#sections that agree $ith the older higher ones resolving the discrepancy. The firstreport &y 9hen et al. used a ne$ method determining the a&sorption cross section

&y o&serving the loss of the dimer in a mass spectrometer as a molecular &eam isexposed to a ;< laser.768This method has the $ea-ness that it can only &e used at

$avelengths $here there are strong laser sources.There has &een another even more recent study $hich sho$s that ma>or revisions inthe ozone depletion model are not necessary. 0n addition to ma-ing ne$measurements @apanastasiou et al. from the N 4arth ystems Ja&oratory 7138hold that the /@J group did not properly account for the uncertainty in their modelingof the cross#sections and that $hen this is done correctly the /@J error estimates$ould encompass the other results although the central estimate remains muchsmaller. ther studies are under$ay and should &e pu&lished shortly. @reliminaryresults from the nderson group at Carvard presented at the 2336 I; 9onferencesupport the higher a&sorption cross#sections. These ne$ experiments motivated &y

the /@J result have significantly improved our -no$ledge of the 9l dimera&sorption cross#section and increased our confidence in the ozone destructionphotochemical models.

[edit] Observations on ozone layer depletion

The most pronounced decrease in ozone has &een in the lo$er stratosphere. Co$everthe ozone hole is most usually measured not in terms of ozone concentrations at theselevels ($hich are typically of a fe$ parts per million) &ut &y reduction in the totalcolumn ozone a&ove a point on the 4arth5s surface $hich is normally expressed in

Fo&son units a&&reviated as GF;G. ?ar-ed decreases in column ozone in thentarcticspring and early summer compared to the early 16*3s and &efore have &een
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o&served using instruments such as the Total zone ?apping pectrometer(T?).7118

Jo$est value of ozone measured &y T?each year in the ozone hole.

Deductions of up to *3 in the ozone column o&served in the austral (southernhemispheric) spring over ntarctica and first reported in 16E' (arman et al. 16E')are continuing.7128Through the 1663s total column ozone in eptem&er and cto&erhave continued to &e %3='3 lo$er than pre#ozone#hole values. 0n therctictheamount lost is more varia&le year#to#year than in the ntarctic. The greatest declinesup to "3 are in the $inter and spring $hen the stratosphere is colder.

Deactions that ta-e place on polar stratospheric clouds (@9s) play an important rolein enhancing ozone depletion.71"8@9s form more readily in the extreme cold ofntarctic stratosphere. This is $hy ozone holes first formed and are deeper over

ntarctica. 4arly models failed to ta-e @9s into account and predicted a gradualglo&al depletion $hich is $hy the sudden ntarctic ozone hole $as such a surprise tomany scientists.7citation needed8

0n middle latitudes it is prefera&le to spea- of ozone depletion rather than holes.Feclines are a&out " &elo$ pre#16E3 values for "'=3ON and a&out for "'=3O. 0n the tropics there are no significant trends.71%8

zone depletion also explains much of the o&served reduction in stratospheric andupper tropospherictemperatures.71'8718The source of the $armth of the stratosphere isthe a&sorption of ;< radiation &y ozone hence reduced ozone leads to cooling. ome

stratospheric cooling is also predicted from increases in greenhouse gasessuch as92L ho$ever the ozone#induced cooling appears to &e dominant.7citation needed8

@redictions of ozone levels remain difficult. The ,orld ?eteorological rganizationIlo&al zone Desearch and ?onitoring @ro>ectPDeport No. %%comes out stronglyin favor for the ?ontreal @rotocol &ut notes that a ;N4@166% ssessmentoverestimated ozone loss for the 166%=166* period.
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Chemicals in the atmosphere

[edit] CCs in the atmosphere

9hlorofluorocar&ons (99s) $ere invented &y Thomas ?idgley /r.in the 1623s.They $ere used in air conditioningcooling units as aerosol spray propellantsprior tothe 16E3s and in the cleaning processes of delicate electronic eAuipment. They alsooccur as &y#products of some chemical processes. No significant natural sources haveever &een identified for these compounds P their presence in the atmosphere is duealmost entirely to human manufacture. s mentioned in the ozone cycle overviewa&ove $hen such ozone#depleting chemicals reach the stratosphere they aredissociated &y ultraviolet light to release chlorine atoms. The chlorine atoms act as acatalyst and each can &rea- do$n tens of thousands of ozone molecules &efore &eingremoved from the stratosphere. Iiven the longevity of 99 molecules recoverytimes are measured in decades. 0t is calculated that a 99 molecule ta-es an averageof 1' years to go from the ground level up to the upper atmosphere and it can staythere for a&out a century destroying up to one hundred thousand ozone moleculesduring that time.71*8

[edit] !erification of observations

cientists have &een increasingly a&le to attri&ute the o&served ozone depletion to theincrease of man#made (anthropogenic)halogencompounds from 99s &y the use ofcomplex chemistry transport models and their validation against o&servational data

(e.g. J0?9T 9Ja?). These models $or- &y com&ining satellite measurementsof chemical concentrations and meteorological fields $ith chemical reaction rateconstants o&tained in la& experiments. They are a&le to identify not only the -eychemical reactions &ut also the transport processes $hich &ring 99photolysis

products into contact $ith ozone.

[edit] "he ozone hole and its causes
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zone hole in North merica during 16E% (a&normally $arm reducing ozonedepletion) and 166* (a&normally cold resulting in increased seasonal depletion).ource: N71E8

The ntarctic ozone hole is an area of the ntarctic stratosphere in $hich the recent

ozone levels have dropped to as lo$ as "" of their pre#16*' values. The ozone holeoccurs during the ntarctic spring from eptem&er to early Fecem&er as strong$esterly $inds start to circulate around the continent and create an atmosphericcontainer. ,ithin thispolar vortexover '3 of the lo$er stratospheric ozone isdestroyed during the ntarctic spring.7168

s explained a&ove the primary cause of ozone depletion is the presence of chlorine#containing source gases (primarily 99s and related halocar&ons). 0n the presence of;< light these gases dissociate releasing chlorine atoms $hich then go on tocatalyze ozone destruction. The 9l#catalyzed ozone depletion can ta-e place in the gas

phase &ut it is dramatically enhanced in the presence ofpolar stratospheric clouds

(@9s).7238

These polar stratospheric clouds(@9) form during $inter in the extreme cold. @olar$inters are dar- consisting of " months $ithout solar radiation (sunlight). The lac- ofsunlight contri&utes to a decrease in temperature and thepolar vortextraps and chillsair. Temperatures hover around or &elo$ #E3 O9. These lo$ temperatures form cloud

particles. There are three types of @9 cloudsL nitric acid trihydrate clouds slo$lycooling $ater#ice clouds and rapid cooling $ater#ice(nacerous) cloudsL that providesurfaces for chemical reactions that lead to ozone destruction. 7218

Thephotochemicalprocesses involved are complex &ut $ell understood. The -eyo&servation is that ordinarily most of the chlorine in the stratosphere resides in sta&leGreservoirG compounds primarily hydrochloric acid (C9l) and chlorine nitrate(9lN2). Furing the ntarctic $inter and spring ho$ever reactions on the surfaceof the polar stratospheric cloud particles convert these GreservoirG compounds intoreactive free radicals (9l and 9l). The clouds can also remove N2from theatmosphere &y converting it to nitric acid $hich prevents the ne$ly formed 9l from

&eing converted &ac- into 9lN2.

The role of sunlight in ozone depletion is the reason $hy the ntarctic ozonedepletion is greatest during spring. Furing $inter even though @9s are at their most

a&undant there is no light over the pole to drive the chemical reactions. Furing thespring ho$ever the sun comes out providing energy to drive photochemicalreactions and melt the polar stratospheric clouds releasing the trapped compounds.,arming temperatures near the end of spring &rea- up the vortex around mid#Fecem&er. s $arm ozone#rich air flo$s in from lo$er latitudes the @9s aredestroyed the ozone depletion process shuts do$n and the ozone hole closes.7228

?ost of the ozone that is destroyed is in the lo$er stratosphere in contrast to themuch smaller ozone depletion through homogeneous gas phase reactions $hichoccurs primarily in the upper stratosphere.72"8

[edit] #nterest in ozone layer depletion
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,hile the effect of the ntarctic ozone hole in decreasing the glo&al ozone isrelatively small estimated at a&out % per decade the hole has generated a great dealof interest &ecause:

The decrease in the ozone layer $as predicted in the early 16E3s to &e roughly

* over a 3 year period.7citation needed8 The sudden recognition in 16E' that there $as a su&stantial GholeG $as $idely

reported in the press. The especially rapid ozone depletion in ntarctica hadpreviously &een dismissed as a measurement error.72%8

?any7citation needed8$ere $orried that ozone holes might start to appear over otherareas of the glo&e &ut to date the only other large#scale depletion is a smallerozone GdimpleG o&served during the rctic spring over the North @ole. zoneat middle latitudes has declined &ut &y a much smaller extent (a&out %='decrease).

0f the conditions &ecame more severe (cooler stratospheric temperatures morestratospheric clouds more active chlorine) then glo&al ozone may decrease ata much greater pace. tandard glo&al $armingtheory predicts that thestratosphere $ill cool.72'8

,hen the ntarctic ozone hole &rea-s up the ozone#depleted air drifts out intonear&y areas. Fecreases in the ozone level of up to 13 have &een reported in

Ne$ Qealand in the month follo$ing the &rea-#up of the ntarctic ozone hole.728

[edit] Conse$uences of ozone layer depletion

ince the ozone layer a&sor&s;


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ecause it is this same ;< radiation that creates ozone in the ozone layer from 2(regular oxygen) in the first place a reduction in stratospheric ozone $ould actuallytend to increase photochemical production of ozone at lo$er levels (in thetroposphere) although the overall o&served trends in total column ozone still sho$ adecrease largely &ecause ozone produced lo$er do$n has a naturally shorter

photochemical lifetime so it is destroyed &efore the concentrations could reach alevel $hich $ould compensate for the ozone reduction higher up.7citation needed8

[edit] &iological effects

The main pu&lic concern regarding the ozone hole has &een the effects of increasedsurface ;< and micro$ave radiation on human health. o far ozone depletion inmost locations has &een typically a fe$ percent and as noted a&ove no directevidence of health damage is availa&le in most latitudes. ,ere the high levels ofdepletion seen in the ozone hole ever to &e common across the glo&e the effects could

&e su&stantially more dramatic. s the ozone hole over ntarctica has in someinstances gro$n so large as to reach southern parts of ustraliaNe$ Qealand9hilergentina and outh frica environmentalists have &een concerned that the increasein surface ;< could &e significant.72E8

[edit] 'ffects on humans

;


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". Cortical CataractsP tudies are suggestive of an association &et$een ocularcortical cataractsand ;


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fter a 16* report &y the ;.. National cademy of ciencesconcluded that credi&lescientific evidence supported the ozone depletion hypothesis7"68a fe$ countriesincluding the ;nited tates 9anada $eden Fenmar- and Nor$ay moved toeliminate the use of 99s in aerosol spray cans.7%38t the time this $as $idelyregarded as a first step to$ards a more comprehensive regulation policy &ut progress

in this direction slo$ed in su&seAuent years due to a com&ination of political factors(continued resistance from the halocar&on industry and a general change in attitudeto$ards environmental regulation during the first t$o years of the Deaganadministration) and scientific developments (su&seAuent National cademyassessments $hich indicated that the first estimates of the magnitude of ozonedepletion had &een overly large). The ;nited tates &anned the use of 99s in aerosolcans in 16*E.7%38The 4uropean 9ommunity re>ected proposals to &an 99s in aerosolsprays and in the ;.. 99s continued to &e used as refrigerants and for cleaningcircuit &oards. ,orld$ide 99 production fell sharply after the ;.. aerosol &an &ut

&y 16E had returned nearly to its 16* level.7%380n 166" Fu@ontshut do$n its 99facility.7%18

The ;.. Iovernment5s attitude &egan to change again in 16E" $hen ,illiamDuc-elshausreplaced nne ?. urfordas dministrator of the ;nited tates4nvironmental @rotection gency.;nder Duc-elshaus and his successor JeeThomas the 4@ pushed for an international approach to halocar&on regulations. 0n16E' 23 nations including most of the ma>or 99 producers signed the


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process for su&stances other than methyl &romide and under the 9ritical ;se4xemption (9;4) process for methyl &romide. ee Iareau7%%8and Fe9anio and

Norman7%'8for more detail on the exemption processes.

To some extent 99s have &een replaced &y the less damaging hydro#chloro#fluoro#

car&ons (C99s) although concerns remain regarding C99s also. 0n someapplications hydro#fluoro#car&ons (C9s) have &een used to replace 99s. C9s$hich contain no chlorine or &romine do not contri&ute at all to ozone depletionalthough they are potent greenhouse gases. The &est -no$n of these compounds is

pro&a&ly C9#1"%a (D#1"%a) $hich in the ;nited tates has largely replaced 99#12 (D#12) in automo&ile air conditioners. 0n la&oratory analytics (a former GessentialGuse) the ozone depleting su&stances can &e replaced $ith various other solvents.7%8

Ozone Diplomacy &y Dichard enedic- (Carvard ;niversity @ress 1661) gives adetailed account of the negotiation process that led to the ?ontreal @rotocol. @iel-eand etsillprovide an extensive revie$ of early ;.. government responses to the

emerging science of ozone depletion &y 99s.

?ore recently policy experts have advocated for efforts to lin- ozone protectionefforts to climate protection efforts.7%*87%E8?any F are also greenhouse gasses somesignificantly more po$erful agents of radiative forcing than car&on dioxide over theshort and medium term. @olicy decisions in one arena affect the costs andeffectiveness of environmental improvements in the other.

[edit] )rospects of ozone depletion

zone#depleting gas trends.

ince the adoption and strengthening of the ?ontreal @rotocol has led to reductions inthe emissions of 99s atmospheric concentrations of the most significant compoundshave &een declining. These su&stances are &eing gradually removed from the

atmospherePsince pea-ing in 166% the 4ffective 4Auivalent 9hlorine (449l) levelin the atmosphere had dropped a&out 13 &y 233E. 0t is estimated that &y 231' the
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ntarctic ozone hole $ill have reduced &y 1 million -mR out of 2' (Ne$man et al.233%)L complete recovery of the ntarctic ozone layer is not expected to occur untilthe year 23'3 or later. ,or- has suggested that a detecta&le (and statisticallysignificant) recovery $ill not occur until around 232% $ith ozone levels recovering to16E3 levels &y around 23E.7%68The decrease in ozone#depleting chemicals has also

&een significantly affected &y a decrease in&romine#containing chemicals. The datasuggest that su&stantial natural sources exist for atmospheric methyl &romide(9C"r).7'38The phase#out of 99s means that nitrous oxide(N2) $hich is notcovered &y the ?ontreal @rotocol has &ecome the most highly emitted ozonedepleting su&stance and is expected to remain so throughout the 21st century.7'18

,hen the 233% ozone hole ended in Novem&er 233% daily minimum stratospherictemperatures in the ntarctic lo$er stratosphere increased to levels that are too $armfor the formation of polar stratospheric clouds (@9s) a&out 2 to " $ee-s earlier thanin most recent years.7'28

The rctic $inter of 233' $as extremely cold in the stratosphereL @9s $erea&undant over many high#latitude areas until dissipated &y a &ig $arming event$hich started in the upper stratosphere during e&ruary and spread throughout therctic stratosphere in ?arch. The size of the rctic area of anomalously lo$ totalozone in 233%#233' $as larger than in any year since 166*. The predominance ofanomalously lo$ total ozone values in the rctic region in the $inter of 233%#233' isattri&uted to the very lo$ stratospheric temperatures and meteorological conditionsfavora&le for ozone destruction along $ith the continued presence of ozonedestroying chemicals in the stratosphere.7'"8

233' 0@99summary of ozone issues concluded that o&servations and modelcalculations suggest that the glo&al average amount of ozone depletion has no$approximately sta&ilized. lthough considera&le varia&ility in ozone is expected fromyear to year including in polar regions $here depletion is largest the ozone layer isexpected to &egin to recover in coming decades due to declining ozone#depletingsu&stance concentrations assuming full compliance $ith the ?ontreal @rotocol.7'%8

Temperatures during the rctic $inter of 233 stayed fairly close to the long#termaverage until late /anuary $ith minimum readings freAuently cold enough to produce@9s. Furing the last $ee- of /anuary ho$ever a ma>or $arming event senttemperatures $ell a&ove normal P much too $arm to support @9s. y the time

temperatures dropped &ac- to near normal in ?arch the seasonal norm $as $ella&ove the @9 threshold.7''8@reliminary satellite instrument#generated ozone mapssho$ seasonal ozone &uildup slightly &elo$ the long#term means for the NorthernCemisphere as a $hole although some high ozone events have occurred.7'8Furing?arch 233 the rctic stratosphere pole$ard of 3O North Jatitude $as free ofanomalously lo$ ozone areas except during the three#day period from 1* ?arch to 16$hen the total ozone cover fell &elo$ "33 F; over part of the North tlantic regionfrom Ireenland to candinavia.7'*8

The area $here total column ozone is less than 223 F; (the accepted definition of the&oundary of the ozone hole) $as relatively small until around 23 ugust 233. ince

then the ozone hole area increased rapidly pea-ing at 26 million -mR 2% eptem&er.0n cto&er 233Nreported that the year5s ozone hole set a ne$ area record $ith
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a daily average of 2 million -mR &et$een * eptem&er and 1" cto&er 233L totalozone thic-nesses fell as lo$ as E' F; on E cto&er. The t$o factors com&ined 233sees the $orst level of depletion in recorded ozone history. The depletion is attri&utedto the temperatures a&ove the ntarctic reaching the lo$est recording sincecomprehensive records &egan in 16*6.7'E87'68

n cto&er 233E the 4cuadorian pace gencypu&lished a report called C0@4D0Na study of the last 2E years data from 13 satellites and dozens of ground instrumentsaround the $orld among them their o$n and found that the ;< radiation reachingeAuatorial latitudes $as far greater than expected clim&ing in some very populatedcities up to 2% ;


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[edit] "he +owland-(olina hypothesis

0n 16*% ran- her$ood Do$land 9hemistry @rofessor at the ;niversity of9alifornia at 0rvine and his postdoctoral associate ?ario /. ?olinasuggested thatlong#lived organic halogen compounds such as 99s might &ehave in a similar

fashion as 9rutzen had proposed for nitrous oxide./ames Joveloc-(most popularly-no$n as the creator of the Iaia hypothesis) had recently discovered during a cruisein the outh tlantic in 16*1 that almost all of the 99 compounds manufacturedsince their invention in 16"3 $ere still present in the atmosphere. ?olina andDo$land concluded that li-e N2 the 99s $ould reach the stratosphere $here they$ould &e dissociated &y ;< light releasing 9l atoms. ( year earlier Dichardtolars-i and Dalph 9iceroneat the ;niversity of ?ichigan had sho$n that 9l is evenmore efficient than N at catalyzing the destruction of ozone. imilar conclusions$ere reached &y?ichael ?c4lroyand teven ,ofsyat Carvard ;niversity. Neithergroup ho$ever had realized that 99s $ere a potentially large source ofstratospheric chlorine P instead they had &een investigating the possi&le effects ofC9l emissions from the pace huttle $hich are very much smaller.)

The Do$land#?olina hypothesis$as strongly disputed &y representatives of theaerosol and halocar&onindustries. The 9hair of the oard of Fu@ont$as Auoted assaying that ozone depletion theory is Ga science fiction tale...a load of ru&&ish...utternonsenseG.7%28Do&ert &planalp the @resident of @recision


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[edit] "he ozone hole

The discovery of the ntarctic Gozone holeG &y ritish ntarctic urveyscientistsarman Iardinerand han-lin(announced in a paper inNaturein ?ay 16E') cameas a shoc- to the scientific community &ecause the o&served decline in polar ozone

$as far larger than anyone had anticipated.72%8atellite measurements sho$ingmassive depletion of ozone around the south pole$ere &ecoming availa&le at thesame time. Co$ever these $ere initially re>ected as unreasona&le &y data Aualitycontrol algorithms (they $ere filtered out as errors since the values $ere unexpectedlylo$)L the ozone hole $as detected only in satellite data $hen the ra$ data $asreprocessed follo$ing evidence of ozone depletion in in situo&servations. ,hen thesoft$are$as rerun $ithout the flags the ozone hole $as seen as far &ac- as 16*.728

usan olomon an atmospheric chemist at the National ceanic and tmosphericdministration (N) proposed that chemical reactions onpolar stratosphericclouds(@9s) in the cold ntarctic stratosphere caused a massive though localizedand seasonal increase in the amount of chlorine present in active ozone#destroyingforms. The polar stratospheric clouds in ntarctica are only formed $hen there arevery lo$ temperatures as lo$ as #E3 degrees 9 and early spring conditions. 0n suchconditions the ice crystals of the cloud provide a suita&le surface for conversion ofunreactive chlorine compounds into reactive chlorine compounds $hich can depleteozone easily.

?oreover thepolar vortexformed over ntarcticais very tight and the reaction $hichoccurs on the surface of the cloud crystals is far different from $hen it occurs inatmosphere. These conditions have led to ozone holeformation in ntarctica. This

hypothesis $as decisively confirmed first &y la&oratory measurements andsu&seAuently &y direct measurements from the ground and from high#altitudeairplanes of very high concentrations of chlorine monoxide (9l) in the ntarcticstratosphere.7"8

lternative hypotheses $hich had attri&uted the ozone hole to variations in solar ;orhalocar&onproducing nations agreed to phase out production of 99s halons andrelated compounds a process that $as completed in 166.

ince 16E1 the ;nited Nations 4nvironment @rogrammehas sponsored a series ofreports on scientific assessment of ozone depletion &ased on satellite measurements.The 233* report sho$ed that the hole in the ozone layer $as recovering and thesmallest it had &een for a&out a decade.7%8The 2313 report found that Gver the pastdecade glo&al ozone and ozone in the rctic and ntarctic regions is no longerdecreasing &ut is not yet increasing... the ozone layer outside the @olar regions is

pro>ected to recover to its pre#16E3 levels some time &efore the middle of this
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century... 0n contrast the springtime ozone hole over the ntarctic is expected torecover much later.G7'8

[edit] Ozone depletion and global warming

There are five areas of lin-age &et$een ozone depletion and glo&al $arming:

Dadiative forcingfrom various greenhouse gasesand other sources. The same 92radiative forcing that produces glo&al $arming is expected to

cool the stratosphere.78This cooling in turn is expected to produce a relativeincreaseinozone(") depletion in polar area and the freAuency of ozoneholes.7*8

9onversely ozone depletion represents a radiative forcing of the climatesystem. There are t$o opposing effects: Deduced ozone causes thestratosphere to a&sor& less solar radiation thus cooling the stratosphere $hile

$arming the troposphereL the resulting colder stratosphere emits less long#$ave radiation do$n$ard thus cooling the troposphere. verall the coolingdominatesL the 0@99 concludes that Gobserved stratosphericO3losses overthe past two decades have caused a negative forcing of the surface-

troposphere systemG71'8of a&out S3.1' 3.13$attsper sAuare meter (,mR).7E8

ne of the strongest predictions of the greenhouse effect is that thestratosphere $ill cool.78lthough this cooling has &een o&served it is nottrivial to separate the effects of changes in the concentration of greenhousegasesand ozone depletion since &oth $ill lead to cooling. Co$ever this can

&e done &y numerical stratospheric modeling. Desults from theNational

ceanic and tmospheric dministration5s Ieophysical luid FynamicsJa&oratorysho$ that a&ove 23 -m (12.% miles) the greenhouse gasesdominate the cooling.768

s noted under 5@u&lic @olicy5 ozone depleting chemicals are also oftengreenhouse gases. The increases in concentrations of these chemicals have

produced 3."% 3.3" ,mR of radiative forcing corresponding to a&out 1%of the total radiative forcing from increases in the concentrations of $ell#mixed greenhouse gases.7E8

The long term modeling of the process its measurement study design oftheories and testing ta-e decades to document gain $ide acceptance andultimately &ecome the dominant paradigm. everal theories a&out the

destruction of ozone $ere hypothesized in the 16E3s pu&lished in the late1663s and are currently &eing proven. Fr Fre$ chindell and Fr @aul
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Ne$man N Ioddard proposed a theory in the late 1663s using aI0rigin 2333supercomputer that modeled ozone destruction accounted for*E of the ozone destroyed. urther refinement of that model accounted forE6 of the ozone destroyed &ut pushed &ac- the estimated recovery of theozone hole from *' years to 1'3 years. (n important part of that model is the

lac- of stratospheric flight due to depletion of fossil fuels.)

[edit] (isconceptions about ozone depletion

fe$ of the more common misunderstandings a&out ozone depletion are addressed&riefly hereL more detailed discussions can &e found in the ozone#depletion B.

99s are Gtoo heavyG to reach the stratosphere

0t is commonly &elieved that 99 molecules are heavier than air (nitrogen or oxygen)

so that the 99 molecules cannot reach the stratosphere in significant amount.7*38

utatmospheric gases are not sorted &y $eightL the forces of $ind can fully mix the gasesin the atmosphere. Fespite the fact that 99s are heavier than air and $ith a longlifetime they are evenly distri&uted throughout the tur&osphereand reach the upperatmosphere.7*18

?an#made chlorine is insignificant compared to natural sources

nother misconception is that Git is generally accepted that natural sources oftropospheric chlorine are four to five times larger than man#made oneG. ,hile strictlytrue troposphericchlorine is irrelevantL it isstratosphericchlorine that affects ozonedepletion. 9hlorine from ocean sprayis solu&le and thus is $ashed &y rainfall &eforeit reaches the stratosphere. 99s in contrast are insolu&le and long#lived allo$ingthem to reach the stratosphere. 0n the lo$er atmosphere there is much more chlorinefrom 99s and related haloal-anesthan there is in C9l from salt spray and in thestratosphere halocar&ons are dominant .7*28nly methyl chloride $hich is one of thesehalocar&ons has a mainly natural source 7*"8and it is responsi&le for a&out 23 percent

of the chlorine in the stratosphereL the remaining E3 comes from man made sources.
http://en.wikipedia.org/wiki/SGI_Origin_2000http://en.wikipedia.org/wiki/SGI_Origin_2000http://en.wikipedia.org/wiki/SGI_Origin_2000http://en.wikipedia.org/w/index.php?title=Ozone_depletion&action=edit&section=20http://www.faqs.org/faqs/ozone-depletionhttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-69%23cite_note-69http://en.wikipedia.org/wiki/Turbospherehttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-70%23cite_note-70http://en.wikipedia.org/wiki/Salt_sprayhttp://en.wikipedia.org/wiki/Haloalkanehttp://en.wikipedia.org/wiki/Haloalkanehttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-71%23cite_note-71http://en.wikipedia.org/wiki/Ozone_depletion#cite_note-72%23cite_note-72http://en.wikipedia.org/wiki/File:Sources_of_stratospheric_chlorine.pnghttp://en.wikipedia.org/wiki/File:Sources_of_stratospheric_chlorine.pnghttp://en.wikipedia.org/wiki/SGI_Origin_2000http://en.wikipedia.org/wiki/SGI_Origin_2000http://en.wikipedia.org/w/index.php?title=Ozone_depletion&action=edit&section=20http://www.faqs.org/faqs/ozone-depletionhttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-69%23cite_note-69http://en.wikipedia.org/wiki/Turbospherehttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-70%23cite_note-70http://en.wikipedia.org/wiki/Salt_sprayhttp://en.wikipedia.org/wiki/Haloalkanehttp://en.wikipedia.org/wiki/Ozone_depletion#cite_note-71%23cite_note-71http://en.wikipedia.org/wiki/Ozone_depletion#cite_note-72%23cite_note-72


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ect C9l into the stratosphere &ut researchers 7*%8

have sho$n that the contri&ution is not significant compared to that from 99s. similar erroneous assertion is that solu&le halogen compounds from the volcanic

plume of ?ount 4re&uson Doss 0sland ntarctica are a ma>or contri&utor to thentarctic ozone hole.7*%8

n ozone hole $as first o&served in 16'

I.?.. Fo&son(4xploring the tmosphere 2nd 4dition xford 16E) mentionedthat $hen springtime ozone levels over Calley ay$ere first measured in 16' he$as surprised to find that they $ere U"23 F; a&out 1'3 F; &elo$ spring levelsU%'3 F; in the rctic. These ho$ever $ere at this time the -no$n normalclimatological values &ecause no other ntarctic ozone data $ere availa&le. ,hatFo&son descri&es is essentially the baselinefrom $hich the ozone hole is measured:actual ozone hole values are in the 1'3=133 F; range.

The discrepancy &et$een the rctic and ntarctic noted &y Fo&son $as primarily amatter of timing: during the rctic spring ozone levels rose smoothly pea-ing inpril $hereas in the ntarctic they stayed approximately constant during earlyspring rising a&ruptly in Novem&er $hen the polar vortex &ro-e do$n.

The &ehavior seen in the ntarctic ozone hole is completely different. 0nstead ofstaying constant early springtime ozone levels suddenly drop from their already lo$$inter values &y as much as '3 and normal values are not reached again untilFecem&er.7*'8

The ozone hole should &e a&ove the sources of 99s

ome people thought that the ozone hole should &e a&ove the sources of 99s.Co$ever 99s are $ell mixed in the troposphereand the stratosphere. The reasonfor occurrence of the ozone hole a&ove ntarctica is not &ecause there are more 99sconcentrated &ut &ecause the lo$ temperatures help form polar stratospheric clouds.7*8

0n fact there are findings of significant and localized Gozone holesG a&ove other partsof the earth.7**8

The Gozone holeG is a hole in the ozone layer

There is a common misconception that Vozone holeW is really a hole in the ozonelayer.,hen the Gozone holeG occurs the ozone in the lo$er stratosphere is destroyed.The upper stratosphere is less affected so that the amount of ozone over the continentdecreases &y '3 percent or even more. The ozone hole does not disappear through thelayerL on the other hand it is not a uniform 5thinning5 of the ozone layer. 0t is a GholeG$hich is a depression not in the sense of Ga hole in the $indshield.G

[edit] ODS re$uirements in the (arine industry

0? has amended ?D@J nnex


23/33

s from 1 /uly 2313 all vessels $here ?D@J nnex


24/33

. chiermeier B (eptem&er 233*). G9hemists po-e holes in ozone theoryG(7dead lin$8).Nature001(*11): "E2=".doi:13.13"E%%6"E2a. @?0F1*E6E*2%.http:$$$.nature.comne$s233*3*362%full%%6"E2a.html.

*. rancis F. @opeL /aron 9. CansenL \yle F. ayesL Dandall D. riedlLtanley @. ander (233*). G;ltraviolet &sorption pectrum of 9hlorine

@eroxide 9l9lG.. %hys. &hem. '///(23): %"22="2.doi:13.1321>p3*3$. @?0F1*%*%*2".http:pu&s.acs.orgdoia&s13.1321>p3*3$.

E. ulletinPThe >ournal of the ,orld ?eteorological rganization6. 9hen C] Jien 9] Jin ,] Jee ]T Jin // (?ay 2336). G;< a&sorption

cross sections of 9l9l are consistent $ith ozone degradation modelsG.!cience.20('62E): *E1=%. doi:13.112science.11*1"3' .@?0F16%2"E2'.http:$$$.sciencemag.orgcgipmidloo-upXvie$Ylong^pmidY16%2"E2'.

13. Fimitrios \. @apanastasiouL p63'"%'.

11. The zone Cole Tour: @art 00. Decent zone Fepletion12. ,orld ?eteorological rganization (,?)1". ;.. 4@: zone Fepletion1%. _ abhttp:$$$.epa.govozonesciencemythsglo&[dep.html1'. _ abG9limate 9hange 2331: ,or-ing Iroup 0: The cientific asisG.

(ntergovernmental %anel on &limate &hange)or$ *roup (. 2331. pp. 9hapter.% tratospheric zone. http:$$$.grida.noclimateipcc[tar$g122".htm.

1. 7181*. 4ncyclopedia.com: chlorofluorocar&ons1E. http:eartho&servatory.nasa.gov0TFvie$.phpXidY1**116. ntarctic zone Cole23. ntarctic ozone#depletion B section *21.

http:$$$.atmos.$ashington.eduUdavidcT?211articles[optionalToon[Turco61[ozone.pdf

22. zone Cole ,atch2". . her$ood Do$land (26 ?ay 233). Gtratospheric ozone depletionG.

%hil. +rans. ,. !oc. B.3/(1%6): *6=*63. doi:13.136Erst&.233'.1*E".@?0F12*26%. @?9136%32.

http:rst&.royalsocietypu&lishing.orgcontent"11%6*6.full. G%. reeradical reactions for ozone removal: Deaction %.1G.2%. _ abtephen 9. Qehr (Novem&er 166%).Gccounting for the zone Cole:

cientific Depresentations of an nomaly and @rior 0ncorrect 9laims in @u&licettingsG. +he !ociological uarterly.4(%): 3"=16. doi:13.1111>.1'""#E'2'.166%.t&33%16.x.http:$$$.>stor.orgpss%121'21 .

2'. G9limate 9hange 2331: ,or-ing Iroup 0: The cientific asisG.(ntergovernmental %anel on &limate &hange)or$ *roup (. 2331. pp. 9hapter6.".2 @atterns of uture 9limate 9hange.http:$$$.grida.nopu&licationsotheripcc'tarXsrcYclimateipcc[tar$g1"'1.htm.

2. http:people.oregonstate.eduUmuirpstratozo.htm
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"'. 9ruic-shan-s \/ \lein 4 \lein D (Fecem&er 1662).G;ltraviolet lightexposure and lens opacities: the eaver Fam 4ye tudyG.'m %ublic 0ealth62(12): 1'E=2. doi:13.213'/@C.E2.12.1'E. @?0F1%'"%2.@?916%'%2.http:$$$.a>ph.orgcgipmidloo-upXvie$Ylong^pmidY1%'"%2.

". ,est \ ?uoz chein F Funcan FF Du&in I (Fecem&er 166E).GDacial differences in lens opacities: the alis&ury 4ye 4valuation (44)

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"E. D. @. inhaL . 9. ingh and F.#@. Cbder (1666). G@hotoecophysiology ofcyano&acteriaG.ournal of %hotochemistry and %hotobiology.: 61=131."6. National cademy of ciences(16*).0alocarbons2 effects on

stratospheric ozone.,ashington F9. http:&oo-s.google.comXidYa2]r]/^dAYCalocar&ons:+4ffects+on+tratospheric+zone.

%3. _ abcd?orrisette @eter ?. (16E6).GThe 4volution of @olicy Desponses totratospheric zone FepletionG.Natural ,esources ournal21: *6"=E23.http:$$$.ciesin.orgdocs33"#3333"#33.html. Detrieved 2313#3%#23.

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%%. Iareau / (2313). G critical revie$ of the successful 99 phase#out versusthe delayed methyl &romide phase#out in the ?ontreal @rotocolG.
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