Ale[andra Carcla

1he Cxford School

29/11/2011
Atmospheiic Chemistiy
Introduct|on

efore we sLarL developlng Lhls Loplc we need Lo deflne whaL aLmospherlc chemlsLry
ls 1hls ls a speclflc camp lnslde chemlsLry LhaL ls cenLred on Lhe sLudy of Lhe
aLmospherlc condlLlons and speclally Lhelr chemlc composlLlon A more speclflc answer
of whaL Loplc aLmospherlc chemlsLry sLudy ls LhaL lL lnclude Lhe emlsslon LransporL
and deposlLlon of aLmospherlc chemlcal specles also Lhe raLes and mechanlsms of
chemlcal reacLlons LhaL are Laklng place ln Lhe aLmosphere and Lhe effecLs of
aLmospherlc specles on humans and Lhere healLh Lhe blosphere and Lhe weaLher

1hls ls a Loplc LhaL has been broadly sLudled because of lLs vlLal lmporLance ln 1993 a nobel
rlze was awarded Lo aul ! CruLzen Marlo ! Mollna and l Sherwood 8owland for Lhelr
work ln aLmospherlc chemlsLry parLlcularly concernlng Lhe formaLlon and
decomposlLlon of ozone 1he lmporLance of Lhls sLudy relays on Lhe lncreaslng
polluLlon LhaL has been creaLed by Lhe human klnd and LhaL ls affecLlng Lhe ozone layer
LhaL proLecLs Lhe planeL from Lhe harmful solar rays and oLher dangers 1haL sLudy of
ozone formaLlon and decomposlLlon helps us Lo deLermlne why Lhe ozone layer ls
deLerloraLlng ln some polnLs and how Lhls can be sLopped or aL leasL slow down

tmospher|c ||fet|me

ALmospherlc llfeLlme ls deflned as Lhe mean Llme LhaL a molecule resldes ln Lhe
aLmosphere before lL ls removed by chemlcal reacLlon or decomposlLlon 1he
aLmospherlc llfeLlme measures Lhe Llme scale on whlch changes ln Lhe producLlon or
loss raLes of a specles may be expecLed Lo LranslaLe lnLo changes ln Lhe specles
concenLraLlon 1he aLmospherlc llfeLlme can also be compared Lo Lhe Llme scales for
aLmospherlc LransporL Lo lnfer Lhe spaLlal varlablllLy of a specles ln Lhe aLmosphere
specles wlLh llfeLlmes longer Lhan a decade Lend Lo be unlformly mlxed whlle specles
wlLh shorLer llfeLlmes may have slgnlflcanL gradlenLs reflecLlng Lhe dlsLrlbuLlons of
Lhelr sources and slnks

MeLhane Slnks
Cnce emlLLed meLhane ls removed from
Lhe aLmosphere by a varleLy of processes
frequenLly called slnks 1he balance
beLween meLhane emlsslons and meLhane
removal processes ulLlmaLely deLermlnes
aLmospherlc meLhane concenLraLlons and
how long meLhane emlsslons remaln ln Lhe
aLmosphere 1he domlnanL slnk ls oxldaLlon
by chemlcal reacLlon wlLh hydroxyl radlcals (CP) MeLhane reacLs wlLh CP Lo produce
CP
3
and waLer ln Lhe Lropospherlc layer of Lhe aLmosphere SLraLospherlc oxldaLlon
plays a mlnor role ln removlng meLhane from Lhe aLmosphere Slmllar Lo Lropospherlc
oxldaLlon mlnor amounLs of meLhane are desLroyed by reacLlng wlLh CP ln Lhe
sLraLosphere 1hese Lwo CP reacLlons accounL for almosL 90 of meLhane removals ln
addlLlon Lo meLhane reacLlon wlLh CP Lhere are Lwo oLher known slnks mlcroblal
upLake of meLhane ln solls and meLhane's reacLlon wlLh chlorlne (Cl) aLoms ln Lhe
marlne boundary layer lL ls esLlmaLed Lhese slnks conLrlbuLe 7 and less Lhan 2 of
LoLal meLhane removal respecLlvely

Creenhouse Cases
Carbon uloxlde released from combusLlon of fossll fuels equlllbraLes among Lhe
varlous carbon reservolrs of Lhe aLmosphere Lhe ocean and Lhe LerresLrlal blosphere
on Llmescales of a few cenLurles Powever a slzeable fracLlon of Lhe CC
2
remalns ln
Lhe aLmosphere awalLlng a reLurn Lo Lhe solld earLh by much slower weaLherlng
processes and deposlLlon of CaCC
3
Common measures of Lhe aLmospherlc llfeLlme of
CC
2
lncludlng Lhe efoldlng Llme scale dlsregard Lhe long Lall lLs neglecL ln Lhe
calculaLlon of global warmlng poLenLlals leads many Lo underesLlmaLe Lhe longevlLy of
anLhropogenlc global warmlng Pere we revlew Lhe pasL llLeraLure on Lhe aLmospherlc
llfeLlme of fossll fuel CC
2
and lLs lmpacL on cllmaLe and we presenL lnlLlal resulLs from
a model lnLercomparlson pro[ecL on Lhls Loplc 1he models agree LhaL 2033 of Lhe
CC
2
remalns ln Lhe aLmosphere afLer equlllbraLlon wlLh Lhe ocean (220 cenLurles)

reenhouse effect

MeLhane ls Lhe second mosL abundanL
carbon specles ln Lhe aLmosphere and an
lmporLanL greenhouse gas lL ls emlLLed by
anaeroblc decay of blologlcal carbon (for
example ln weLlands landfllls and
sLomachs of rumlnanLs) by explolLaLlon of
naLural gas and coal and by combusLlon lL
has a mean llfeLlme of 12 years agalnsL
aLmospherlc oxldaLlon by Lhe hydroxyl (CP)
radlcal lLs prlnclpal slnk

Many hydrocarbons oLher Lhan meLhane are emlLLed Lo Lhe aLmosphere from
vegeLaLlon solls combusLlon and lndusLrlal acLlvlLles 1he emlsslon of lsoprene P
2
CC
(CP
3
) CPCP2 from declduous vegeLaLlon ls parLlcularly slgnlflcanL nonmeLhane
hydrocarbons have generally shorL llfeLlmes agalnsL oxldaLlon by CP (a few hours for
lsoprene) so LhaL Lhelr aLmospherlc concenLraLlons are low 1hey are mosL lmporLanL
ln aLmospherlc chemlsLry as slnks for CP and as precursors of Lropospherlc ozone
organlc nlLraLes and organlc aerosols

Carbon monoxlde (CC) ls emlLLed
Lo Lhe aLmosphere by combusLlon
and lL ls also produced wlLhln Lhe
aLmosphere by oxldaLlon of
meLhane and oLher hydrocarbons
lL ls removed from Lhe aLmosphere
by oxldaLlon by CP wlLh a mean
llfeLlme of 2 monLhs Carbon
monoxlde ls Lhe prlnclpal slnk of
CP and hence plays a ma[or
role ln regulaLlng Lhe oxldlzlng
power of Lhe aLmosphere

nlLrous oxlde (n
2
C) ls of envlronmenLal lmporLance as a greenhouse gas and as Lhe
sLraLospherlc precursor for Lhe radlcals nC and nC
2
1he prlnclpal sources of n
2
C Lo
Lhe aLmosphere are mlcroblal processes ln solls and Lhe oceans Lhe maln slnks are
phoLolysls and oxldaLlon ln Lhe sLraLosphere resulLlng ln an
aLmospherlc llfeLlme for n
2
C of abouL 130 years

AbouL 90 of LoLal aLmospherlc ozone (C
3
) resldes ln Lhe
sLraLosphere where lL ls produced by phoLolysls of C
2
1he
ulLravloleL phoLons ( 240 nm) needed Lo phoLolyze C
2
are
LoLally absorbed by ozone and C
2
as solar radlaLlon Lravels
Lhrough Lhe sLraLosphere As a resulL ozone concenLraLlons
ln Lhe Lroposphere are much lower Lhan ln Lhe
sLraLosphere


tratosphere and 1roposphere

1he sLraLosphere ls Lhe second
ma[or layer of LarLhs aLmosphere
[usL above Lhe Lroposphere and
below Lhe mesosphere lL
ls sLraLlfled ln LemperaLure wlLh
warmer layers hlgher up and
cooler layers farLher down 1hls ls
ln conLrasL Lo Lhe Lroposphere
near Lhe LarLhs surface whlch ls
cooler hlgher up and warmer
farLher down 1he border of Lhe
Lroposphere and sLraLosphere Lhe Lropopause ls marked by where Lhls lnverslon
beglns whlch ln Lerms of aLmospherlc Lhermodynamlcs ls Lhe equlllbrlum level 1he
sLraLosphere ls slLuaLed beLween abouL 10 km (6 ml) and 30 km (30 ml) alLlLude above
Lhe surface aL moderaLe laLlLudes whlle aL Lhe poles lL sLarLs aL abouL 8 km (3 ml)
alLlLude WlLhln Lhls layer LemperaLure lncreases as alLlLude lncreases
(see LemperaLure lnverslon) Lhe Lop of Lhe sLraLosphere has a LemperaLure of abouL
270 k (-3C or 296l) [usL sllghLly below Lhe freezlng polnL of waLer

1he Lroposphere ls Lhe lowesL
porLlon of LarLhs aLmosphere lL
conLalns approxlmaLely 80 of
Lhe aLmospheres mass and 99 of
lLs waLer vapor and aerosols 1he
average depLh of Lhe Lroposphere
ls approxlmaLely 17 km (11 ml) ln
Lhe mlddle laLlLudes lL ls deeper ln
Lhe Lroplcs up Lo 20 km (12 ml)
and shallower near Lhe olar
8eglons aL 7 km (43 ml) ln
summer and lndlsLlncL ln wlnLer

1he lowesL parL of Lhe Lroposphere where frlcLlon wlLh Lhe LarLhs surface lnfluences
alr flow ls Lhe planeLary boundary layer

1ropospherlc ozone plays a cenLral role ln aLmospherlc chemlsLry by provldlng Lhe
prlmary source of Lhe sLrong oxldanL CP lL ls also an lmporLanL greenhouse gas ln
surface alr ozone ls of greaL concern because of lLs LoxlclLy Lo humans and vegeLaLlon
Czone ls supplled Lo Lhe Lroposphere by slow LransporL from Lhe sLraLosphere and lL ls
also produced wlLhln Lhe Lroposphere by a chaln reacLlon lnvolvlng oxldaLlon of CC
and hydrocarbons by CP ln Lhe presence of nC

Czone producLlon by Lhls mechanlsm

ls parLlcularly rapld ln urban areas where emlsslons of nC

and of reacLlve
hydrocarbons are hlgh

Sulfurlc acld produced ln Lhe aLmosphere by oxldaLlon of sulfur dloxlde (SC
2
) ls a ma[or
componenL of aerosols ln Lhe aLmosphere and an lmporLanL conLrlbuLor Lo acld
deposlLlon Sources of SC
2
Lo Lhe aLmosphere lnclude emlsslon from combusLlon
smelLers and volcanoes and oxldaLlon of oceanlc dlmeLhylsulflde (CP
3
)
2
S emlLLed by
phyLoplankLon lL ls esLlmaLed LhaL abouL 73 of LoLal sulfur emlsslon Lo Lhe
aLmosphere ls anLhropogenlc

Concluslon