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Vogt et al. (1996)

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Vogt et al.

(1996),

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,

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Vogt et al. (1996)

^:;=

Sander and Crutzen (1996)

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.

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Waschewsky (1998)

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Vogt et al. (1996).

x\=

Mochida et al. (1998a)

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NaCl).

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x\=

Mochida et al. (1998b)

>?A@?AC2UWGHC2;<L ;HGuC2=KmSRSi<E?V=]L

Cl 2

^>? EZHGapS?_CP=:<i :<;= c<ZE=:<i pP;@iE<E=];

EOh>;SC2JKmP=K; >B2E; E?

Knudsen cell reactor,

^[RPd:;uG ^gSC2= ^D e<RSYERSgcD"ED

Cl 2

^{YmVD^?VJ} ^E?

e;<R;S^OF^2d

Br 2 .

x\=

Behnke et al. (1997)

>?V@B_CVD"E;uG CVDuG ;HGHCPJ]mRS;ED y

2

^x

5

^>? ^pS;@iEE=]; EOh>;SC2JKmP=]; :=

B2mS?V=]n2;uG CVDuG e<;RS;^OF^Pd

ClNO 2 ,

^? ^GaU ^:;= ^Y=

Seisel et al. (1997)

>?2@BACAD"E;HG CADaG ;HGHCPJKmSRS;<ESD C2YSZ y0x

3

^>? ^ECP?PRS?2i

NaCl

^:<;=

KBr.

=]; ESDF>;lGuCP=:d ;uGHCPJ]mRS;ED ^S=K; CVDuG :f<RS=]; ;@YP^YlGbYSfMPY BjGqOXESD CPOQG pP;@iEE=]OwG

EOh>;SC2=KmPJKOwG

,

^C2Y

Cl - ,

^?VJ^Ga;= ^D ;Se?2@?AZpPBPROXESD

HCl,

^ECADbG ^;B2RS=]; ^c<iED

,

^;Se<g ^;ZSCPi >B2E<O gn2=GHD"L

;HGuC2=N:;SCPiESCP;ED"L

.

^x ^n2B2; ^=N:;uGbi ^{^S=}

’

^;ZSC2d ^CADbG ;uGHC2=N:;C2i<ESC2;<ED ?VJGb;= C2;

HNO 3 , H 2 SO 4 , MSA

^:<;=

YnP;@=:g YnVf

(Kerminen et al. (1998)).

x\=

Ingham et al. (1999)

e;RYSZEJN;<E;HG :<=GuDC2=N:i mS?VmY>B Gb; :;= >=K; pP?2OhR2DCP=:d >?A@B_CVD eiuGaO ESCAD EDF>;HGuC2=:gSCVDCP; CAD"L ;HGHCPJ]mR;ED<L C2YZ

DMS

^>?

BrO,

^D ^YSeYJK; ^{e;RiS^S?2=}

DMSO

^:;=

?VJGb;= Y EfuGamP?2E<>YL CADFL MVDI>?VJK;L CPYSZ pS?VJKYSZ >? ;ZSCVd CPOwG ;@YS^SglGaOwG

.

(11)

x\=

Solomon et al. (1994), Davis et al. (1996)

^:<;=

Vogt et al. (1999)

B2mP?2=NnP;HG gSCP= CPY

=KUXmP=KY >SeYRS?VJ Ga; :<;SCP;ESCSRSB{?V= CSRSYPe<YEc";=KRS=N:g gTVYkG

,

^?2JNC2? i<>?2E; >? CP=]L RJ]T2?2L :";= _x

,

^?VJNCP?

BP><>?2E; mP=]gPC2= ;ZnSilGb?2= CVDbG ?jGa?2RP^SYPe<YJND"ESD CPYSZ M2@OXRSJ]YSZ :<;= C2YZ [ROh>JNYZ

.

^zwGaU ^Y=

Schweitzer et al. (1999)

>?V@B_CVD"E;uG >? ?PR2^S;<ESCVD"RS=K;S:<i e<?V=KRi<>;C2; CP=]L ?AC2?PRSYP^?jGa?VJKL ;HGuC2=KmSRSi<E?V=KL Gb=NCSRO{mSUwG

;@YS^SYlGbYSfMSOwG ?jGaUXE?POwG >? mS=];@f<>;C2; y

aBr

^:;=

NaI

e<;<RiS^YkGHCS;L >YRS=K;S:i ;@YP^glGb; :<;= Y=

Keene et al. (1998)

B2mP?2=]nP;HG C2DuG ?VnPiR2C2D"ESD CPYPZ >PD<MP;HGa=KE<>YSf ? Gb?PR2^SYSeYJND"ED"L CPYPZ [ROh>JKYPZ ;e<g

C2Y

pH.

^v ?jGa?2R2^YPe<YJD"ED C2YSZ

Br

^{^=N;}

pH 5.5

^BPO{L

3

e<;R;<>BjGa?V= EMS?VmSglG ;<>?AC2i<[S@PDCVD

,

^E?

;HGuC2JKpP?PESD >? ;ZSCAd CPYSZ MP@O{RSJKYSZ D YSeYJK; ;ZnPilGa?V= ED">;uGHC2=:<i :<;pSUXL C2Y

pH

>?2=]UwGb?ACP;=

.

x\= >?_CPRPd"E?2=]L EOh>;C2=KmPJKOwG ;Seg CPYSZ<L

Ayers et al. (1999)

^EC2Y

Cape Grim (

^t Z<ECPR;@J];

)

:;= C2Y GHDFEJ

Macquarie

^ESC2YHG ^y0gPC2=]Y 0;S^Oh>B`GaY \:?2;HGbg ZeYECVD"RSJKTAYZlG C2YSZL >SDMS;lGb=KE<>YPfL

;Se<?V@?AZpSB2ROXED"L M2@OXRSJKYSZ :;= [ROX>JKYSZ ;Se<g pS;@iEE=K; EOh>;SC2JKmP=K;

,

^mP=KgPC2= B2mP?2=NnS;lG >?2JKOXESD ESCPY

@gS^SY

Br - /Na +

^E? ^2DFR;E">BjGa; pS;@iEE=K; EOh>;SCPJ]mS=]; E? EMPBPESD >? CVD pPi@;EE;

.

x\=

Rudolph et al. (1996)

[S;E=]T2g>? GbY= ECP; =KEYTfS^=]; C2YSZ ;=KpS;HGbJKYPZ :<;= C2YZ C2?ACPR;M2@OXRSY;=]pS;HGaJNYSZ

,

^C2; YPe<YJK; ;HGuC2=KmSRYPfHG >?

Cl

^e<YS@Sf C2;MVfSCP?2R; ;eg gPC2= >? RJ]TV?2L xhv

,

Ze<YS@gS^S=KE;HG >=]; >BPED CPRSYSeYE<c<;=KRS=N:d EZ^2:BjGHCSRO{ED

Cl

^CVD"L ^CPinADFL ^CPOwG

10 3 atoms/cm 3

^:;=

e<RgPC2?2=Ga;lG gSC2= E? e<;S^P:gE<>=]; :@J}>;S:<; Y= >BPE?2L EZS^2:<?jGuCPRUhE?V=KL

Cl

^pS; ^dC2;uG ^eYS@f ^>=:"RSB2L ^S=K;

Ga; EZHGa;S^OQGb=KEC2YflG C2=KL RSJKTV?VL xhv :";= Ga; ?_eD"RS?2iEYSZHG CVDbG Yn2?2=KmPOIC2=:d =N:<;lGagPCAD<C2; CAD"L

CPRYPegEc<;=]R;L

.

v ;HGbJNM Ga?AZ<ESD ?jGa?2R2^UQG ;@YP^SYlGbYSfMSOwG ? GaUXE?2OQG ESCVDuG ;B2RS=K; c<iED ?VJGb;= m2fE:Y@SD @gP^O

CPOWG M;>SD<@UQG C2YZL EZS^P:? GHCPRUXE?POQG

.

^=K; ^;eg ^CV=KL ^e<=]Y ^;HGa=NM Gb?VfE=}>?PL ?jGaUXE?V=KL ;ZSCPYSf C2YSZ

?VJKmPYZL ?2JGq;= CPY

BrO

^eYZ >SeYR?VJ Ga; >?ACPR2DFpP?VJ MSR2DFE=}>YPe<Y=KUwGuCP;L c<;E">;SCPYE:<YPeJ]; mP=];c"YRS=N:d"L YPeC2=N:d"L ;eYRRSgcDFED<L

(DOAS).

t

RP:<?AC2i >?A^i@?2L EZ^2:<?jGHCSRUXE?V=KL

BrO (20-30 pmol/mol)

;HGa=MkGb?VfpVD:;HG ESCPY

t

RP:CP=N:g ESCSRUh>; ;HGai<>=KnVD"L :<;SCPi CAD mP=]iRS:?2=N; CPYPZ eYS@=:<YSf :;@YP:<;=KRS=KYSf

,

Y= YPeYJ]?2L eiHGuC2; EZHGamSBVYkGuC2;uG >? mSR;>;C2=:BPL ;Se<UI@?V=K?2L gTAYHGHC2YL

( Platt and Moortgat (1999)).

x\=

Alicke et al. (1999)

^>? >?_CSR2d"E?V=KL mP=K;c"YRS=N:dFL c";<E>;C2YE:YPe<J];L YSeC2=:d<L

;Se<YRRgcD"ED"L >?A^Si@PD"L mS=N;mRSY<>Pd"L

(LP-DOAS)

^ECSY

Mace Head

^CVD"L RS@;HGamPJK;L

,

BVmS?V=Kn2;HG gSC2=

Y= EZ^2:<?`GHCSRUXE?V=KL CSOQG RS=KTVUwG x cCPiuGbYSZuG E? ?AeJNe?VmSY =N:<;HGbg

(6 ppt)

^{^S=K;} ^Ga; e<;JNnPYSZHG EDI>;HGuC2=:g Rg@Y ECVDuG M2DF>?2J]; CPYSZ

r\sFt

.

(12)

7

2.2.

Br Cl

s

CPY EMVdI>;

2

^c<;J^GbYHGHCP;= ^Y= ^:f:@Y= ^C2YZ [ROh>JNYZ

,

^CPYPZ MP@OXRSJ]YSZ :<;= CPYPZ

DMS

^ESCPY ^rhsFt

(Vogt et al (1996)).

s

ZHGaYPeC2=N:i

,

[S@BAeYSZ<>? gPCP= Y= RPJKTV?PL [ROh>JNYZ eYPZ e<;Ri^SYkGuC2;= ECVDuG ;BPRS=K;

c"iED

,

Yn2?2=]mUwGbYkGbC2;= E?

HBr

^:";=

HOBr,

^CS; ^YPeYJ]; ^BVMPYSZuG ESC2;<pP?2RB2L

Henry (K H ) ** , 1.3

^:";=

93 M/atm

;HGuC2JKESCPY=]MP;

,

^:<;= ?2=]E<BVRSMSYkGuCP;= ESCADaG ZS^RPd

/

EOX>;C2=KmP=K;S:d c<i<ESD

.

^zF:<?VJ ^CPY

HOBr

;HGuC2=KmSRi

>? =KgkGuCP; MS@OXRSJKYSZ

,

;S:<YS@YZpSUwGuC2;L CADaG ;lGHCPJ]mRS;ED

HOBr + Cl - + H +

BrCl + H 2 O (k 1 =5.6E9 M -2 s -1 )

:= gSMP= CVDuG ;HGHCPJ]mR;ED

HOBr + Br - + H +

Br 2 + H 2 O (k 2 =1.6E10 M -2 s -1 )

?_e<?V=KmVd Y @gP^YL

Br - /Cl -

^?VJ^Ga;=

1/700

^:;= ^Y= C2;M2fSCVDCP?2L CPOQG ;HGuC2=KmSRiE?POwG CVD<L JKmP=K;L CPinAD"L

(k 1 /k 2 = 0.35),

e";RSi^SYlGuC2;<L

BrCl

^C2Y ^YSeYJKY ^C2?V@=N:i ^{e;RiS^?V=} >YRS=K;S:<g [RUh>=]Y

.

HOBr + Cl - + H +

BrCl + H 2 O BrCl + Br -

Br 2 Cl -

Br 2 + Cl -

Net: HOBr + H + + Br -

H 2 O + Br 2

Br 2

(0.76

/atm)

^"! ^#$% ^! ^!'&)( ^%+*-, ^.'/0$1 ^2'%+*-, ^! ^$'^! 3"4)2'*

!5&

%6078,9%

!":

,

;

%4

!'&"(

3=<>%5?@4)2

&=!

25*

,

^; ^! ^,- ^! ^& ^*0/1 ^$'@A+7B, ^C0$5< ^;5D^'.

.

^EF%20 ^''. ^; ^; ^! ^! ^.'% ^)! ^% ^! ^6'. ⁽ ^; ^G,H*

G,I$/'

& D

*=25* %'. C5$'<

;5D

'.

,

^* ^& ^D^! ^& ^$'/0$'4"3"J%

!

!5&"(

%

: &)!

$

!' 45%<

!

,H%@?'$'4"20+

:

(Sander and Crutzen (1996)):

Br 2 + hv

2Br

2 ( Br + O 3 )

2 ( BrO + O 2 ) 2 ( BrO + HO 2 )

2 ( HOBr + O 2 )

Net: 2HO 2 +

^K

r 2 + 2O 3 + hv

^L

2HOBr + 4O 2 + H 2 O

**

M'N'OP5Q9R9S OT UWV RYXOV UWVZ

Henry

^V ^[+X+\JV] ^`_VaaVbc`S+] UWQHR _Z+\dTeRfUJa+g=_TJQ9R Uih] SjWa+^S] d'S+^ Uih] Z+\+aJk'] P5l_+h]

TWcRHS+^ _+UJSmTJaX] \^S Sa+S^X nJ^`l+[+ZOS

.

^op

= c a /c g ,

^XbVZ

c a

^h _+Z\JdjeRYUWaQ"_+h _UqhfR Z+\+aJk P0l_+h dS^

c g

^_+UihrR ^{S+jJa^`S}

.

stu'vxw

y{z)|5}

~

u

y{z)|'}

(13)

,

, HOBr

HOCl,

u

/

^| ^w ^vvxw ^z)|'}

,

^| ^z ^|5} ^w ^v ^z ^|} ^! ^|'}

S (IV)

|

S (VI) (

^} ^w

w

"

v#

|

v

$ "

vxv

v

),

^v ^w)u5w ^z ^w ^v'u ^z"| ^v

:

SO 3 2- + HOCl

^L

HSO 4 - + Cl - SO 3 2- + HOBr

^L

HSO 4 - + Br -

H

^w)u5w

BrCl

^|+} ^u'

/

^| ^% ^w ^vv@w ^z"|'} ^w)v ^} ^t ^|} ^w)tu'vxw

,

^&('

(0,94

⁾

/atm),

u | tu

v v@w

*

v

t

}0

w

v #

u'v+!#

u

,

w0v

u

%,

,

t |

}

vz)|

w | +}

:

BrCl + hv

^L

Br + Cl

-.

w $

w0v

|

w v u +

Cl

^w0v

Br

^w ^v,5u ^/0 ^u ^w ^v ^t ¹ ^# ^| ^v

w

| # w t w 2

w0v 3

w

|

v w

HCl

w)v

HBr,

.

.:

Cl + CH 4 + O 2

^L

HCl + CH 3 OO

Br + HCHO + O 2

^L

HBr + CO + HO 2

(14)

9

2.3.

|

w

3

^w ^$ ^w0v ^/ ^v ^| ^s

(Vogt et al (1999)).

^v,#%v

w

! "

u#

w0v

|}

w)tu'v@w

z"|'}

w

+}

v

z)|

w

|'} w

, v

.

v u +

w v'u

/

u

+

w0v

w"u z'

u +

,

^| ^w ^," ^|5} ^v ^u ⁺

Cl

^w0v

Br

u

/ w w

| z)|

2 w

5u

z

$"

u5w

.

v u +

1

tu

}

vxw

|

w0v

| w

v

w0v

*

w w

} v

u

w +

.

^& ^w ^w ^| ^u ⁺ ^t

w v'u

z"|

(

=Cl, Br, I)

w0v

DMS.

IO + ClO

^L

I + Cl + O 2 IO + BrO

^L

I + Br + O 2

IO + IO

^L

I 2 + O 2

^L

I 2 O 2

IO + CH 3 SCH 3

^L

I + CH 3 SOCH 3

2

(

^&('

=450 M/atm)

^w0v ²

Br

^!^w ^v ^z

,

^v^| ^tu ^w0v ^|+}

u

/

^| ^w ^vvxw ^z)|5} ^v ^! ^w ^v,5u ^z ^v ^w ^w ^|+} ^w ⁺ ^w

ICl, IBr

^w)v

2 .

+ Cl - + H +

^L

ICl + H 2 O

+ Br - + H +

^L

IBr + H 2 O

+

- + H +

^L

I 2 + H 2 O

s t v # | v

! tu

w0v

|+}

w0tu5vxw

z"|'}

(

v

|

w

"

u't

&(' w w

tu

w)v

w)u5w

z

)

w)v 0 t u +

, Cl

^w0v

Br.

^| ^v ^w ^z ^$ ^w0v ^} ^| ^t û ^|0} û ^# û'v+!#

w

v

t w

z

$ w0v

w0v } w w | u

+

.

^t ^t ^v

2

w " # w)v

,

^v^| ^tu ^w0v ^|} ^u' ^z0|5}

,

^v# ^$ ^w0v ^w0v ^w"u ^z5 ^v ^z ^v ^'v ^z

v

w

(

3 -

),

w

w w

!/

}

/

u'vxw w

v

| w |

% w

vxw

.

I 2 O 2 + H 2 O

^L

HOI + IO 2 - + H + IO + IO + H 2 O

^L

HOI + IO 2 - + H +

IO 2 - + H 2 O 2

^L

IO 3 - + H 2 O

~ u

y{z"|'}

~

u

y{z)|5}

stu'v@w

y{z"|'}

(15)

v | w

"

u5t

Henry

¹ ^# ^| ^v ^w ^$ ^w0v ^| ^w)u5w ^z ^w ^w

.

3

|'}

&('

(M/atm) HI (+ H 2 O) H + + I - ( )

IO 450

HOI 450

INO 2 HOI + HNO 2 ( )

INO 3 HOI + HNO 3 ( )

2 3.0

ICl 110

IBr 24

I 2 O 2 HOI + H + + IO 2 -

( )

(16)

11

2.4.

3

!#"$%"$&!('*) !,+!-'* .,' /&0&.*12!,'43 *)657/%8 "*'&9:3<;=3 !,"- /%)3<"- *.,/2+(> ?3@'*

9A" $ <3 !,"$&" *$',B-C $%' -52':34$&'-8 &A"! )3@':3?$%", ,/ &+-' /7)

(Stutz et al (1999)):

D

.,' E

,

^F

= Cl, Br, I.

!-+*!-'-8 G *"(0(HI:3</7 JK *" ".(' ,)6" A57K=3 ML !,", L

2 (

^9A" ^434$,0-/

!,"*'&+?34$%", L

O x ),

^{12$ ,} "43<"(0*1N3@/2$&"- 3@" /7)3@", O0*"43?$7P!*8 (/ "%!-$%P!,1&8 .,/ *6'*J&1%8

,

^.,' "$%1&8 '*

)A57/&8 .,"*' -AI,57'43 $&68 0*P!&$%//&8 $&Q0*1%8 $%'-8

.

^R/S$C ^-/%68 ^.(/ ^&)6' ^,/ ⁴³ ^{," (0} ^0*/

"*6>-0,$&!('+,8 *.,'-'&9 (0-'+,8 1&/%6T&":3 &$& 0*/79"*+$%/ !,"*$%" *$*'-B-C -57':34$&'*8 /2.,$ *9&JI43@/2$&"-

0-1 ,; $&;=3 "?34$&I ,/%;=3

BrO + BrO

^!,"-

BrO + ClO (Sander and Crutzen (1996)).

O

^!,+*!-'-8 ^U -"(0-HI?3@/% JK " .("' -)A" L

x

^!(", ^/7)3<"- V0*"434$%P!,8 ,/ .,/ *P'*J&1%8 0-/ -"-)6' 9*/%;V9",B(!,'*+ .-I$%',8

.

WXVYVZ#[(\

]

Net : O 3 XO x , HO x 2 O 2

X + O 3

^{^}

XO + O 2 (2)

_`

+

^a ^`

2

^{^}

HOX + O 2 (6)

a

`_

+ hv

^{^}

X + OH (7) OH + Z

^{^}

HO 2 + Z’ (8)

hv

bdc,e*f

g

,

^h

= Cl, Br, I,

ⁱ

=

^j

3 , RH

^k(l-m ⁱ

’=

^j

2 , R.

noqpqrVsOtu

vw

+ hv

^x

X + Y (1) 2 (X + O 3 )

^x

2 (XO + O 2 ) (2) 2 (Y + O 3 )

^x

2 (YO + O 2 ) (3) XO + YO

^x

X + Y + O 2 (4) XO + YO

^x

XY + O 2 (5)

Net : 4O 3

XO x ,YO y

6O 2

hv

noqpqrVsOtu

vw

+ hv

^x

X + Y (1) 2 (X + O 3 )

^x

2 (XO + O 2 ) (2) 2 (Y + O 3 )

^x

2 (YO + O 2 ) (3) XO + YO

^x

X + Y + O 2 (4) XO + YO

^x

XY + O 2 (5)

vw

+ hv

^x

X + Y (1) 2 (X + O 3 )

^x

2 (XO + O 2 ) (2) 2 (Y + O 3 )

^x

2 (YO + O 2 ) (3) XO + YO

^x

X + Y + O 2 (4) XO + YO

^x

XY + O 2 (5)

Net : 4O 3

XO x ,YO y

6O 2 Net : 4O 3 hv

XO x ,YO y

6O 2

hv

(17)

e i

= CO

^l ^l

(8)

^l%m ^k,m ^e ^k*k ^e ^&l-m

:

! !"

#

Net : O 3

XO x , HO x

O 2

X + O 3

^$

XO + O 2 (2)

%'&

+

⁽ ^&

2

^$

HOX + O 2 (6)

(

&)%

+ hv

^$

X + OH (7) OH + CO + O 2

^$

HO 2 + CO 2 (8)

hv

* f+

,-

f

&k

./7m

.

l e e e

01

./1

(Reactive Halogen Species, RHS),

^e ^k*k ^e

^l-m ^c ^m^e ^l ^c(e ^2-l%mPk3 &m*l6l k,l%l

e4

3

e e

.

* 0l!2!-

f

%k!

./7m

RHS,

ê ^k*k ê ^%l,m ^c ^mê ^,2,l ^&m^k!

.

⁵

l

c(e

62-l&mk6%l 1

e

kk1

7%ll-m e mc l c

7m8,l13

(

c

-

)

^k,l-m

67&l13

(

^l ^c ^.7m8

)

^. ^l ^e ¹

^l ^c ^l ^f ^e ^k,m ^c,e ^2- ¹ ^l ^c ⁶ ^l2 ⁴ ^l-m8*l

.

9m e c

4

l

26-

(Vogt et al (1999))

- %m7&l

&m k,l,m e m l

8

e

m:0

e m kk

e m

e*f

m1/

e*f

6

l-m 2*l

&mk e mAl

k,ll e4

3 ef

e

.

^;<-m ^e ^m^c ^*m6l ^0l!2!-

f

%k

.=%m > e

k*k e

&l-m

:

I + O 3

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(18)

13

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(19)

2.5.

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(20)

15 CH 3 SCH 3 + Cl

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(21)

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