-
, 2008
2
1: 4 1.1 4 1.2 1.2.1
1.2.2 1.2.3 1.2.4 1.2.5 2:
3:
3.1 3.2 3.3 3.4 3.5 3.6 ,
3.6.1 (CO) 3.6.2 (SO2) 3.6.3 (2) () 3.6.4 (O3) 3.6.5 3.6.6 3.6.7 (Pb)
4:
4.1 4.1.1 ( ) 4.1.2 4.1.3 4.1.3 4.2 4.3 4.3.1 4.3.2 4.4
5: 5.1
2008
3
5.2 O3 NOx VOC 5.3 5.4
6: A 6.1 A -
6.2 (CO, CO2) 6.3 (3)
6.4 (NOx) 6.5 (SO2) 6.6 (volatile organic
compounds, VOCs)
6.7 6.8 6.9 Laser: Lidar
2008
4
1:
1.1
,
, ,
, 4 6
.
() (e).
, ,
(CO2), (2), (2) .
,
, .
,
,
,
. ,
.
,
,
.
2H2O + hv 2 H2 + O2 (.1.1)
, ,
. ,
, 2 3
.
,
12 2 + 6 C2 + hv C6126 + 62+62 (.1.2)
,
2008
5
. 1
2 .
3
(3)
:
O2 + hv O + O (
6
.
1.1: .
/
N2 0.781 1.6 x 107
O2 0.209 9000
Ar 0.0093 4.5 x 109
H2O 0 0.04 5
CO2 370 ppmv 5
CH4 1700 ppbv 10
H2 550 ppb 4
N2O 320 ppb 150
CO 40 200 ppb 0.2
O3 20 100 ppb
ppmv
0.05
C2H6 1 ppb 0.2
SO2 0.1 ppb 5
NO2 0.1 ppb 2
20
.
100 .
3000
.
2008
7
1.2
1.2.1
(, , ,
)
, .
,
, , .
.
,
.
1.2.2
, ,
. ,
,
.
,
. ,
,
2
. ,
,
. 2 ,
.
2 , 2
(, , ..)
. 2
2008
8
. 2
,
,
2 . 2
. , ,
, C2 (370ppm),
2, (21%) .
, ,
2, .
,
(
) 2
,
, .
1.2.3
49% .
,
. , ,
,
( 1.1).
.
60
, ) ) .
100
105 . ,
(600-1000
). (1-2
).
2008
9
.
.
1.1: , , ,
.
C,
(: , 1999).
, )
38000
) 150
1500
.
.
. ,
(,
, )
.
, (CO2) . CO2
2008
10
.
.
.
:
12 2 + 6 C2 + hv C6126 + 62+62 (.1.2)
,
:
. (h)
, ()
(2 2 [] + 1/2 2). ,
(C2+[] (C2)x).
.
,
, .
( ),
. ,
.
, CO2 ,
.
,
, ,
(, , , ...)
( )
( , ,
, ..)
2008
11
CO2
:
)
2.
) 2
CO2 .
CO2
1.2.
1.2: CO2
Mauna Loa Hawaii.
CO2
, CO2
,
. (, ,
)
, .
CO2
2008
12
,
. , ,
, , ,
.
CO2 ,
1.2,
.
1.2.4
2,
.
.
:
(
)
. , ,
. ,
. ,
,
. ,
,
.
, ,
, DNA. ,
(NH4+)
(NO3-).
, ,
, .
. ,
2008
13
,
, . ,
.
10% , ,
90%.
, , ,
, .
(N2) , ,
. .
, , ,
, 600 ,
. ,
.
,
, .
)
, )
, )
, )
, )
.
1.3
.
,
. , ,
.
.
,
, ,
.
2008
14
, .
, ,
.
,
. ,
.
(-3, +4)
( ,-3, +4)
(-3, +4)
( ,-3, +4)
1.3: . (1) :
Nx . (2) :
NOx, NH3 2 . (3) :
. 2
2 .
. (4) :
2 2 . (5) :
. (6) : x
2 2.
2008
15
1.2.5
,
. .
,
.
/ .
.
.
, .
(H2S)
, ,
.
, 2S SO2,
H2SO4 ( ).
, ,
,
. ,
( ) .
(S0)
. (SO42-)
.
.
(H2S).
. ,
2008
16
. 1.4
.
1.4: .
2008
17
2:
.
.
.
.
.
4 ..
.
(1 ..)
, .
61 ..
1157 ..
.
116
1661
.
,
.
18
. 19
2008
18
,
, , ,
.
1848 1866 1875.
...
(1880)
.
20 (1900-1925)
.
.
20 Dr. Henry Antoine Des Voeux 1905
Fog and Smoke
Smog ( )
Smoke+Fog ( 2.1).
20 (1900-1925)
.
1925-1950
Meuse Valley () 1930 63 , Donora
Pennsylvania () 1948 20 Poza Rica () 1950
Los Angeles
1940
( 2.2). 2.1
.
(1925-1950)
.
Pittsburgh St. Louis
.
2008
19
2.1:
(: , 1999).
1950-1980,
() (1952) (4000 ).
SO2
. Clean Air Act
1962 700 . 1950-1980
,
.
.
1950-1980
.
) , )
SO2 )
x .
.
2008
20
1980
) CO2
, )
) ,
( ,
).
.
2.1: Claude Monet 1899 1901,
.
Monet -
.
2008
2008
21
2.2: Loss Angeles.
22
3:
3.1
,
, ,
,
,
. o
( ) ,
.
,
, .
( )
( ) .
, ,
.
. ,
( )
,
.
,
.
.
,
.
,
, ,
,
. ,
2008
23
.
CO2, CH4, N2O CFCs O3
. CFCs
(UV)
.
.
.
3.2
,
.
.
.
(
). ,
. , ,
:
1. ( , ,
).
2. ( ,
).
2008
24
3. (
).
4. ( ,
).
5. ( ).
6. ( ).
:
(i) ,
(ii) ,
(iii) ,
(iv)
(v)
.
,
.
.
60%
.
10-15%, 10%,
20%
5%. ,
.
.
, ,
.
:
-T
.
2008
25
-T
,
.
-O ,
.
-T : 50% .
.
-Y , ,
, .
-H ,
.
.
-
. .
,
.
,
:
(CO).
(SO2).
o (NO2) ().
.
,
.
3.1
.
2008
26
15 16 48 16
16%
48%
16%
15%
5%
3.1:
.
3.3
.
.
.
.
.
.
,
.
. (
) (..
2008
27
) (.. ) .
:
)
(.. ,
,
),
) (..
, , ),
)
,
)
)
,
) .
3.2
.
.
.
()
.
.
2 10
.
,
, ,
100.
2008
28
.
.
()
.
.
(..
)
.
3.2:
(: . , 1997).
( )
, .
.
2008
29
.
.
.
.
. , oo
.
.
.
.
.
.
,
.
. :
I.
.
II.
,
,
2008
30
II.
:
()
,
.
3.4
.
= /
A B (A B)
( ) :
-d[A]/dt = K [A] (3.1)
.
t=0 [A]=[A]o [A]o
, t=t
[A]=[A]o/2, t= 1/e.
(3.1)
(t) ():
= t = ln(2)/K (3.2)
= = 1/K (3.3)
tk =
1/tk. t (
)
( 1/e
2008
31
)
tk.
tp.
:
) tk > tp:
.
) tk tp:
. rate-
limited,
.
tk
tp
.
3.5
,
.
:
2008
32
(1) H .
.
.
.
(2)
.
(CO),
(SO2)
.
.
(.. -)
PAN
.
(3) 1000 km
.
, ,
.
(4)
.
2008
33
.
(5) H
.
(CFCs)
,
.
.
CO2
.
(CH4), (N2O),
(CFCs HCFCs) (3)
.
:
) 0-
100 m.
, .
)
.
,
, .
2008
34
)
.
,
.
) 5000
km.
Rossby,
.
3.3
.
3.4
.
3.3:
(: , 2005).
2008
2008
35
3.4:
(: , 1999).
36
3.6 ,
:
(CO) (SO2) o (NO2) () (O3) (Pb)
3.6.1 (CO)
, , ,
. CO
CO2 2-4
.
,
,
.
75%
25%.
.
,
.
, .
,
.
2008
37
3.6.2 (SO2)
,
. SO2
SO3
.
(CS), (CS2),
(CH3)2S, (H2S) .
,
, ,
.
, , ,
. SO2
.
0-6% ..
SO2. 0.05% .
,
.
,
.
,
.
3.6.3 (2) ()
2
3.
x 2
2 (..
2008
38
). 2 , , ,
.
. 2
.
(2), (3), (3)
(3-), (2-) (4+).
,
(). 50%
.
,
(2).
(2)
,
. .
,
.
3.6.4 (O3)
, .
,
,
.
(15-50
km) 90%
.
.
20
2008
39
.
10%
, (0-15 km).
,
.
.
good up high, bad nearby ,
( 3.5).
,
(VOCs), (NOx)
.
(VOCs NOx) , ,
.
.
, ().
.
CO2,
.
.
.
1/3
CO2
2008
40
. CO2
.
..
( SO2 H2SO4).
.
.
.
(>140 ppbv) ,
, ,
.
.
,
-
, .
U.S. EPA (United States Environmental Protection Agency -
http://www.epa.gov/oar/oaqps/gooduphigh/)
0.5 . -
32 ppbv (
).
,
.
,
,
, ,
, ,
, , .
2008
41
.
3.5: .
3.6.5
(
).
. 1-4
, 5-6 7
.
.
(, , ) (),
.
,
. , , ,
2008
42
, , ,
CFCs.
.
,
.
,
, ,
.
3.6.6
,
.
, .
, ,
, ,
, .
, . ,
,
.
,
.
0.1-1 mm.
.
.
.
2008
43
.
:
* Aitken 0.001 0.1 m
* 0.1 1m
* > 1 m
* 1-1000 m
* 100 m
* 1-100 m
* > 100 m
.
, ,
(
).
3.6
.
0.2 m
10 m .
, ,
.
0.1-1.0 m
.
.
10 m
. ~10 m
, , .
,
2008
44
.
45
3.6.7 (Pb)
.
.
,
.
.
,
.
.
2008
46
(*) ppmv: (10-6) ppbv: (10-9) pptv: (10-12) (*) .. (molecules/cm3) (*) .. (g/m3) : P V = n R T P = (m/ MB) (R/V) T P = (R/MB) T (1) P , MB , , R (R=8.3143 J K-1 mol-1) P. = / = P/P (2) (1) (2) : = (R/MB) (T/ P) (3)
: 80 g/m3 =27 oC P=1000 mbar,
ppbv. : R= 8.3143 J K-1 mol-1 = 0.08206 L atm K-1 mol-1
MBO3 = 48.
2008
47
4:
4.1
4.1.1 ( )
90%
10% ,
( 4.1).
( 4.2)
(.. ,
) ,
.
70
(
) .
70 80
.
60
( )
.
,
.
NO2, HNO3 PAN .
,
.
2008
48
.
.
4.1: .
(UV)
4.2: .
2008
49
4.1.2
:
2 3O O M O M+ + + (4.1) , 2,
3. ( 20 Km)
. ,
280nm,
: 3
2 ( 424 ) ( )NO hv nm NO O P+ < + (4.2) hv 280 424 nm.
2 :
3 2NO O NO O2+ + (4.3) (4.1), (4.2) (4.3)
, (PSS) (Photostationary Steady
State) ,
:
2 23
[ ][[ ][ ]
]j NO NOOk NO
= (4.1)
k (4.3) j[N2]
2. (4.1), (4.2)
(4.3) 4.3
(A4.3), 2
.
2008
50
4.3:
(4.1), (4.2) (4.3).
2
(4.3) .
. , -
(HO2) - RO2 ( R
), CO
(RH), , 2 (
4.4).
2HO NO OH NO2+ + (4.4) 2RO NO RO NO2+ + (4.5)
2OH CO CO HO+ + 2 (4.6) 2 2OH RH RO H O+ + (4.7)
.
(PSS)
(PSSD) 2
. RH
RO2, ,
2008
51
2
.
.
4.5. (x=NO+NO2)
.
.
4.4: - (HO2)
- RO2 O3-NO-NO2 .
2008
52
(h)
(ppm
v)
(h)
(ppm
v)
(h)
(ppm
v)
4.5: .
4.1.3
20 ,
.
.
19
20
1950 (Zanis, 1999). 4.6
2008
53
20 .
0
10
20
30
40
50
60
1880 1900 1920 1940 1960 1980 2000
(ppb
v)
Pic du Midi (3000 m)
Jungfraujoch (3500 m)
Mont Ventoux (1900 m)
Pfander Mountain (1064 m)
Arosa (1860 m)
Hohenpeisenberg (1000 m)
Zugspitze (3000 m)
Pic du Midi (3000 m)
4.6: 20
(:
Marenco et al., 1994)
(Montsouris) .
( , CO, )
.
1% .
(
)
2008
54
.
.
4.1.3
(40-80 ppb).
- 32 ppb
. 4.7
.
,
,
(53 ppb).
.
,
(, , .)
,
(Zerefos et al., 2002).
.
2008
55
4.7: 28/6/1992
(: J. Fishman, NAS Langley Research Center, Hampton,
Virginia, USA). Dobson Units (DU) 1 DU
0.001 cm . 100
DU
( ) 0.1 cm.
4.2
, ,
, , ..,
, . " "
19
" ".
p ( ) 6,5 5,6
. 4.8 p
(p=7), (p
2008
56
7) (p 7). ,
, pH
( pH -
pH
). p 4,6 4,
p ( 2,4).
140 7
pH
2,2 - 3,0
2,9 - 3,3
6,4 - 7,6
11,0 - 12,0
pH < 3,5
pH < 6
pH < 5
4.8: pH.
(S2) (x)
.
,
( ),
.
1980, ,
,
2008
57
S2 x '
.
S2 x
.
. ,
.
, , 95%
,
.
.
1970 .
,
.
,
,
.
, , '
,
(
). , ,
, , .. .
, 1991 22%
,
, 38%.
,
.
... .
,
,
, .
2008
58
, 1970
1980. ,
.
,
, (CaC3), ,
..
(CaS4), :
CaCO3 + H2SO4 CaSO4 + CO2 + H2O (A4.8)
, ,
, ,
.
,
.
.
,
.
.
4.3
4.3.1
, .
, ,
15 35
. , ,
.. .
200nm
2008
59
300nm (Hartleys band)
( )
(UV).
.
:
+O2+ O3 + (
60
4.1
4.10
25 km 4.1.
-,
.
4.9: .
Chapman
,
.
-
,
.
, , ,
( )
.
:
2008
61
X + O3 XO + O2 (4.12) XO + O X + O2 (4.13)
: O + O3 2 O2
X H, OH, NO Cl
. 4.10
Cl.
4.10: Cl
.
-
.
4.1. ,
,
.
2008
62
4.1:
(: WMO, 1981).
261170120
81578225
328691030
1413681135
-1016531840
-3110242945
-52472550
2+3+2+ClO+2+3 (km)
261170120
81578225
328691030
1413681135
-1016531840
-3110242945
-52472550
2+3+2+ClO+2+3 (km)
4.3.2
, 70,
. Halley Bay
Syowa 1980
.
4.11.
.
,
. 4.12
.
.
, (CFCs), halons,
2008
63
, ,
.
freons.
halons .
.
-
.
4.11: .
20
.
2008
64
4.12:
(Bodeker et al., 2001).
CFCs
(UV)
(Cl).
CH4, 2 2 4.14, 4.15
4.16 HCl, ClONO2 HOCl,
.
- (reservoir
species).
Cl + CH4 HCl + CH3 (4.14) ClO + NO2 + M ClONO2 + M (4.15) ClO + HO2 HOCl + O2 (4.16)
( 4.13)
(< -80 0C)
2008
65
. ,
,
(Polar
Stratspheric Clouds PSCs) 4.14.
4.13:
(: R. Wayne, 1991).
4.14: (:
http://www.nasa.gov/lb/vision/earth/lookingatearth/)
2008
66
.4.17 .
HCl + ClONO2 + (PSCs) Cl2 + HNO3 (4.17)
(
)
(ClO)2:
Cl2 + hv Cl + Cl (4.18) 2 (Cl + O3 ClO + O2 ) (4.19) ClO + ClO + M (ClO)2 + M (4.20) (ClO)2 + hv Cl + Cl + O2 (4.21)
: 23 + Cl2 2Cl + 3O2
(ClO)2 .
ClOx
4.12 4.13
.
4.15.
CFCs
.
(ClO)2 2
.
.
. 4.14
(CH4) (HCl),
4.17
. ,
2008
67
CFCs
,
.
.
4.15:
.
2008
68
.
.
. 4.16
-78 C
.
4.16:
. -78 C
.
2008
69
4.17
.
4.17: - .
1962-1971,
1992-2001
2 2001
15 20 km.
- .
1988-1997,
30 1996.
:
.
.
2008
70
.
:
25 + 2 + (aerosols) 2 3 (4.22) ClONO2+ H2O + (aerosols) HOCl + HNO3 (A4.23)
UV ,
,
.
4.4
To
- 15C.
, -20 oC
.
, ,
, ,
.
Fourier 1822
.
.
2008
71
400.000
280 (ppm),
360 ppm. 750 ppb
1700 ppb ( 4.18).
20 .
4.18:
.
( W m-2)
Radiative Forcing.
Radiative Forcing
2008
72
.
"Radiative Forcing" -
. 4.19
(radiative forcing - Wm-2)
-
(IPCC, 2001). 4.19
60% 20%.
4.19: (radiative forcing - Wm-2)
-
-,
( ) .
.
2008
73
(global warming
potential - GWP) 1 kg
radiative forcing 1
kg CO2 :
,
,
.
.
.
, ,
2,5 CO2
. 10
800
.
Arrhenious 1896,
.
.
,
.
.
.
0.5 0.6 C 1880
4.20,
2100, ,
1.5 4.5C.
, ..
. H
21
2008
74
,
,
.
4.20:
150
.
2008
75
T 100
. ,
.
. ,
.
.
2008
76
5:
5.1
(NOx=NO+NO2), H2O,
(RH),
(VOCs) (C).
. (OH),
,
315 nm (A5.1)
(1D) (A5.2). , (1D)
(3P)
(A5.3).
O3 + hv (
77
- (HO2) - (RO2)
CO (RH)
() (A5.7) (A5.8)
.
HCHO, CH3CHO, CH3CCH3
(Lightfoot et al., 1992).
OH + CO CO2 + HO2 (A5.7) MO , 2 OH + RH RO2 + H2O (A5.8) MO , 2
NOx (NOx50 pptv),
NO2
NO2 - -
(HO2 RO2) (Chameides, 1973, Logan, 1985, Crutzen, 1988, Penkett, 1998).
, NO2
424 nm (A5.12) (A5.13)
(.. 2) (A5.13).
NO2 + hv (
78
O2 + O(3P) + M O2 + M (A5.13)
NO2 ,
,
. ,
(Logan, 1983). NO2 O3
(A5.14).
O3 + NO NO2 + O2 (A5.14)
NO2 2
105
(A5.14) (Brimblecombe, 1986). (A5.12), (A5.13)
(A5.14)
(photostationary steady state, PSS) NO2
( 100 )
NO2 (A5.14)
O3
.
(5.1) .
2 23[ ][[ ]
[ ]]j NO NOO
k NO= (5.1)
k (5.14) j[N2]
2. (PSS)
. -
- (HO2 RO2)
PSS
3-2- ( PSSD)
2008
79
NO2
( A5.15 A5.16).
HO2 + NO OH + NO2 (A5.15) RO2 + NO RO + NO2 (A5.16)
(A5.15) (A5.16)
(A5.14) (de More et al., 1997)
(A5.15) (A5.16)
(A5.14). , HO2 RO2
1000
,
(A5.15) (A5.16)
(A5.14) (Lightfoot et al., 1992). O
(A5.7), (A5.8), (A5.12), (A5.13), (A5.15), (A5.16)
.
, NOx 100 pptv
(Chameides, 1973, Logan, 1985). ,
( ) (O3)
P(O3)
L(O3) (5.2) (5.3), :
P(O3)={ka[HO2] + kb[RO2]}[NO] (5.2) L(O3)= f j(O1D) [O3] + kc[HO2][O3] + kd[O3][OH] (5.3)
ka, kb, kc kd (A5.15), (A5.16),
(A5.4) (A5.5), . f
O(1D) OH
2 2
:
2008
80
][][][
2
2
MkOHkOHk
ffe
e
+= (5.4)
ke kf (A5.2) (A5.3), .
(O3) (5.2) (5.3)
L(O3) (Johnston and
Kinnison, 1998). L(O3)
(5.3)
,
.
- RO
(A5.16) O2 (A5.17a) (A5.17b)
, .
RO + O2 RRCHO + HO2 (A5.17a) RO R + RCHO (A5.17b)
, ,
RO2 - . ,
NO2
. ,
CO
1
CH4 3.5 CH4 ( 2) NMHC
(VOCs) 10-14
(Logan, 1985).
VOCs
5.1.
2008
81
1 CO 3
CO + OH CO2 + H
H + O2 + M HO2 + M
2 C4 3
CH4 + OH CH3 + H2O
CH3 + O2 + M CH3O2 + M
CH3O +O2 HCHO + HO2
2{NO2 + hv (+O2) NO + O3} ---------------------------------------------------
CH4 + 4 O2 + 2 hv HCHO + 2O3 + H2O
NO + HO2 NONO2 + hv NO + O
O + O2 + M O3 ------------------------------------------- CO + 2 O2 + hv CO2 + O3
2 + OH CH3O2 + NO CH3O + NO2
HO2 + NO OH + NO2
KOH 298 K 10 - 12 cm3 molecule -1 s-1
26.3 , - 14.3 O3 66.6 8.5 6.0 2.3 3.5 , 1.2 O3 - 2.1 1.2 0.26 ,
0.009
5.1:
CH4
(HCHO) , (A5.18a, R18b, A5.19,
2008
82
A5.20, A5.21) - 2.
2.
HCHO + hv H2 + CO (A5.18a) HCHO + hv H + HCO (A5.18b)
HCHO + OH HCO + H2O (A5.19) HCO + O2 HO2 + CO (A5.20) H + O2 HO2 (A5.21)
CO CH4
(A5.9), (A5.22) (A5.23) H2O2, CH3OOH HNO3.
HO2 + HO2 H2O2 + O2 (A5.9) HO2 + CH3O2 CH3OOH + O2 (A5.22) OH + NO2 + M HNO3 + M (A5.23)
T HNO3 H2O2 OH
HNO3 H2O2 . ( H2O2
HNO3)
.
. HNO3
NOx,
.
- - (CH3OOH)
OH 2 .
2008
83
. CH3OOH
.
NOx
OH NO2
HNO3 (A5.23) - (A5.9), (A5.10),
(A5.11) H2O2 ( 5.1). 5.2
NOx
- - (HO2 + RO2)
()
HO2 (5.15).
NOx
VOCs ( RH) (Lin
et al., 1988). 5.1 5.3.
0.00E+00
2.00E+05
4.00E+05
6.00E+05
8.00E+05
1.00E+06
1.20E+06
1.40E+06
1.60E+06
1.80E+06
2.00E+06
1 10 100 1000NO (pptv)
reac
tion
rate
(mol
ecul
es c
m-3
s-1
)
-5
0
5
10
15
20
net O
3 pro
duct
ion
(ppb
v/ d
ay)
HO2+HO2OH+NO2net O3 production
5.1:
HO2+HO2 (A5.9), OH+NO2 (A5.23) [NO]
CO-CH4.
2008
84
0
5
10
15
20
25
30
35
40
1 10 100 1000
NO (pptv)
HO
2+R
O2 (
pptv
)
0.00E+00
2.00E+06
4.00E+06
6.00E+06
8.00E+06
1.00E+07
1.20E+07
1.40E+07
OH
(mol
ecul
es c
m-3
)
HO2+RO2OH
5.2: [] [HO2+RO2]
[NO] CO-CH4.
(A5.24) (A5.25) (A5.16)
RO2 NO2,
(RONO2) (RO2NO2),
NO2.
RO2 + NO + M RONO2 + M (A5.24) RO2 + NO2 + M RO2NO2 + M (A5.25)
PAN
()
NOx
. PAN 3.
2008
85
3 PAN (CH3COO2NO2)
C2H6 + OH C 2H5 + H2O
C2H5 + O2 + M C2H5O2 + M C2H5O2 + NO C 2H5O + NO2C2H5O +O2 CH 3CHO + HO2
CH3CHO + OH (+ O2) CH3C(O)O2 + H2O
CH3C(O)O2 + NO2 + M CH3C(O)O2NO2 + M
PAN CH3C(O)O2 NO2
:
CH3C(O)O2 + NO2 + CH3C(O)O2NO2 + (A5.26)
(A5.26)
PAN
NO2
(Penkett Brice, 1986).
PAN 30 25 oC
.
PAN NOx
.
PAN NOy
(NOy=NO+NO2+HNO3+PAN+ )
. PAN 10 pptv 400 pptv
NO2
30 pptv (Wayne, 1991). PAN,
RO2NO2 RONO2 NOx
OH (WMO, 1994).
2008
86
5.2 O3 NOx VOC
NO
(VOCs)
. ,
- ,
NO
VOCs.
(NO > ppbv)
VOCs
NO (Sillman et al., 1990; Sillman, 1995;
Sillman, 2003) ( 5.3).
NO VOCs
OH NO HNO
( A5.23) VOCs,
NO (Kleinmann, 1991).
x
x
x
x
x
2 3
x
O3 NOx VOC
.
O3
NOx VOC
.
VOC/ .x 3 x VOC/x
3 VOC
VOC/x.
VOCs. 3
x. 3
x 3 VOC
VOC x
2008
87
VOC/ NOx VOCs
.
. VOCs ( ,
)
VOCs,
VOCs .
,
. NOx
.
VOC/NOx
3 x..
H . (downwind)
,
3 VOC
( ) 3
x ( ).
NOx VOCs
VOC/x
.
2008
88
5.3: (ppb)
NOx VOC (1012 molecules cm-2 s-1)
. ( )
3
.
VOC NOx (Sillman, 2003).
5.4
RO2
5.5.
2008
89
5.4:
.
RO2
HO2
NO2
+ hv (
90
5.5: RO2
- .
- .
RO2 RO + NO2 +NO
RONO2
+NO
+O2
+NO2
RONO RHO + HNO
RRCO + HO2
R + RCHO
5.3
, .
O3 NO2 (A5.27) NO3
.
NO2 + O3 + M NO3 + O2 (A5.27)
NO3,
NO2, N2O5 (A5.28), N2O5
NO3
HNO3 NOx
HNO3 (Wayne, 1991).
NO2 + O3 + M N2O5 + (A5.28)
2008
91
HCHO NO3
HO2 - (RO2).
NO3
5.6.
NO2 + O3 NO3 NO2 + M
MN2O5 HNO3
+ H2O
+ RH
R
RO2
HNO3
5.6: NO3
.
5..4
O3 HOx (OH+HO2)
. 15%
,
10-7 10-6, Lelieveld Crutzen (1990)
. HO2
(A5.29). HO2 (aq)
+ 2- (A5.30).
HO2 (g) HO2 (aq) (A5.29) HO2 (aq) H + + O2- (A5.30)
2008
92
2- O3 (
O3) HO2 (A5.31) (A5.32 ).
O3 (aq) + O2- 2O2 + OH + OH
- (A5.31) 2HO
HO2 (aq) + O2- H2O2 + O2 + OH
- (A5.32) 2HO
(A5.29) (A5.32) O3
HOx.
-
HO2(g) (A5.15) NO HO2
O3 .
30-40% (Lelieveld Crutzen,
1990)
O3
3% (Liang Jacob, 1997).
2008
93
6: A
6.1 A -
50
.
()
.
: () ()
.
:
.
,
, CO, O3, NO2, SO2
(VOCs).
... :
() ,
() .
.
2008
94
6.2 (CO, CO2)
- (NDIR).
.
CO
CO .
CO ,
.
IR 5.1.
, ,
, .
,
CO.
CO.
.
.
.
, CO
,
CO .
,
.
NDIR
CO2. 2
2. NDIR-CO2
2008
95
N2O . NDIR
,
. (
)
.
6.1: - (Nondispersine infrared analysis,NDIR).
2008
96
6.3 (3)
(UV).
O3
(253.7 nm) 3.
O3
.
3.
. ,
.
.
: , ,
,
.
O3 .
,
,
() . 3
3
.
6.4 (NOx)
NOx
( 5.2). ,
, (5.1),
.
: + 3 2* + 2 (5.1)
,
O2, O .
2008
97
3 3
,
. , x (=NO+NO2),
2
( , ).
2
Ox .
6.2: () x ( 2).
5.2 2,
Ox
.
2008
98
x.
:
( 2), ,
,
. x,
2 .
,
.
. 2
. x, 2,
, 2 .
x .
3
x. 2
(x-NO).
3
2.
6.5 (SO2)
SO2
.
.
SO2 , ,
.
(TCM).
SO2 TCM.
, SO2
SO2.
2008
99
.
548nm SO2.
SO2
.
, , ,
SO2
.
,
, (NDIR-SO2).
SO2
(UV-fluorescence),
(220 nm) SO2
( 320 nm).
SO2 ()
SO2 .
6.6 (volatile organic
compounds, VOCs)
.
1.6 ppm .
100 ( )
10 ( ),
.
: (ppmV)
(ppmC).
. : ()
, () ,
2008
100
(ppmC).
,
: (CH4)
(VOCs).
3 : , .
.
(Gas Chromatography, GC)
(FID).
(mass spectroscopy, MS)
GC .
GC-MS
.
5.3.
6.3: (GC).
2008
101
(VOCs)
, VOCs
-
. CH4 VOCs
( ),
FID.
(certified standards).
,
.
- (FPD),
(ECD) o
(TCD).
FID 2
,
.
FID 1 ppmV
(CH4) 1ppmV ( 2 ppmC) (C2H6). 1 ppmV 1
ppmV ,
FID,
: 2 ppmC 1 ppmC
.
FPD
.
FPD 2 . ,
S2*.
~ 395 nm.
ECD
- . ECD
.
.
.
TCD
.
2008
102
.
6.7
: (i) , (ii)
(iii) .
.
,
(g) (m3).
. , 10
103
) . ,
, .
() .
.
.
,
. ,
, .
. ,
.
.
.. (S).
,
. ( )
,
- (XRF)
(Neutron Activation
Analysis, ).
XRF
-.
.
,
.
,
.
11.
2008
104
,
.
.
6.8
,
. ,
,
..
pH, ( ),
( ).
.
pH, , ,
, ,
. pH
.
.
,
.
.
6.9 Laser: Lidar
Lidar (Laser Identification,
Detection and Ranging)
. ,
,
,
.
2008
105
'60,
().
( 1.5-2 ),
,
(Kunkel et al., 1978).
.
'70,
(dye lasers),
.
, ,
, , , ,
, .
'80 ,
(excimer lasers) Nd:YAG,
(, .) (Milton et
al., 1992)
45 (Ancellet et al., 1989, Papayannis et al., 1990).
Lidar ,
1980 , Lidar
,
3000
(Kiemle et al., 1992).
Lidar
, ,
(Allario et al., 1992).
.
,
mrad.
. ,
2008
106
.
,
.
.
.
Laser. laser
.
LIDAR
. LIDAR
.
LIDAR Laser
.
Laser
.
( )
.
.
,
.
LIDAR. :
- LIDAR Raman:
Raman ,
.
.
- LIDAR :
. .
2008
107
- LIDAR :
.
.
- LIDAR Doppler: Doppler. ,
,
( )
.
( )
( ),
(
).
.
.
- LIDAR :
.
.
.
.
LIDAR .
2008
108
-
.
.
,
(=h, h = Planck
). ,
.
.
-
.
.
.
, (=h)
(, , )
o: +h *.
(*)
.
.
(Infrared Spectroscopy)
.
,
2008
109
() , . H
.
, ()
.
: ,
. .
, ,
, .
:
-
.
-
.
-
, .
.
. .
,
.
.
-
, .
()
(-)
.
2008
110
.
, , .
:
Rayleigh:
.
10% .
,
,
.
. Rayleigh
.
.
.
Mie:
,
.
( , ).
(, , , ).
Raman: - .
,
-
()
. Raman
. Raman.
2008
111
A.
Brimblecombe P., Air composition and chemistry, Cambridge University Press,
second edition, 1996.
Finlayson-Pitts Barbara J. and James N. Pitts, Jr., Chemistry of the Upper and Lower
Atmosphere, Academic Press, 2000.
Fox L. Donald, Boubel W. Richard, Turner D. Bruce and Stern C. Arthur,
Fundamentals of Air Pollution. Third Edition. Academic Press, Inc. 530 pp., 1992.
Hobbs Peter V., Basic Physical Chemistry for the Atmospheric Sciences, Cambridge
University Press, Cambridge, 1995.
Seinfeld J.H. and S.N. Pandis, Atmospheric Chemistry and Physics, Wiley, New
York, 1998.
Wayne R. P., Chemistry of Atmospheres, second edition, Oxford University Press,
Oxford, 1991.
.
., , ,
, , , , 1999.
., ., ., , , University Studio
Press, , 1998.
, ,
, , 2005.
, -
, ,
, 82 ., 2006.
2008
112
, , ,
& , ,
, , , 2006.
,
, , , 2007.
, 1997: , ,
, 52 ., 1997.
, ,
, , , , 1984.
.
Allario F., W. Miller and L. Staton, "NASA Laser Remote Sensing
Programme",SPIE, 1714, 4-19, 1992.
Ancellet G., A. Papayannis, G. Megie, J. Pelon, "Tropospheric Ozone Measurements
Using a Nd:YAG Laser and the Raman Shifting Technique", Journal of Oceanic
and Atmospheric Technology, 6, 832-839, 1989.
Ayers G.P., S.A. Penkett, R.W. Gillet, B. Bandy, I.E. Galbally, C.P. Meyer, C.M.
Elsworth, S.T. Bentley, and B.W. Forgan, 1992: Evidence for photochemical
control of ozone concentrations in unpolluted marine air, Nature, 360, 446-449.
Bodeker, G.E., J.C. Scott, K. Kreher, and R.L. McKenzie, Global ozone trends in
potential vorticity coordinates using TOMS and GOME intercompared against the
Dobson network: 1978-1998, Journal of Geophysical Research, 106 (D19), 23029-
23042, 2001.
Brimblecombe, P., 1986: Air composition and chemistry, Cambridge University
Press.
2008
113
Chameides, W., and J.C.G. Walker, 1973: A photochemical theory of tropospheric
ozone, J. Geophys. Res., 78(36), 8751-8760.
Crutzen, P.J., 1988: Tropospheric ozone: An overview, in Tropospheric ozone, edited
by I.S.A. Isaksen, D. Reidel Publ. Co., 3-32.
De More, W.B., S.P. Sander, C.J. Howard, A.R. Ravishankara, D.M. Golden, C.E.
Kolb, R.F. Hampson, M.J. Kurylo, and M.J. Molina, 1997: Chemical kinetics and
photochemical data for use in stratospheric modeling, evaluation number 12,
National Aeronautics and Space Administration, Jet Propulsion Laboratory, JPL
Publication 97-4.
Johnston, H., and D. Kinnison, Methane photooxidation in the atmosphere: Contrast
between two methods of analysis, J. Geophys. Res., 103(D17), 21,967-21,984,
1998.
IPCC. 2001. Climate change 2001: The scientific basis, Contribution of Working
Group I to the Third Assessment Report of the IPCC. Eds. Houghton, J.T., Ding,
Y., Griggs, D.J., Noguer, M., Van der Linden, P.J., Dai, X., Maskell, K., and
Johnson, C.A., Chapter 2, Observed Climate Variability and Change, p. 99-182,
Cambridge University Press, Cambridge, UK.
Kiemle C., G. Ehret, W. Renger, "Tropospheric water vapour profiling using an
airborne DIAL system: results from the EFEDA '91 experiment", SPIE 1714, 251-
257, 1992.
Kleinman, L.I., 1991: Seasonal dependance of boundary layer peroxide concentration:
The low and high NOx regimes, J. Geophys. Res., 96(D11), 20,721-20,733.
unkel K., E. Eloranta and S. Shipley, "Lidar observations of the convective
Boundary Layer", J. Appl. Meteor., 16, 1306-1311, 1977.
2008
114
Leleiveld, J., and P.J. Crutzen, 1990: Influences of cloud photochemical processes on
tropospheric ozone, Nature, 343, 227-233.
Lin, X., M. Trainer, and S.C. Liu, 1988: On the nonlinearity of the tropospheric ozone
production, J. Geophys. Res., 93(D12), 15,879-15,888.
Lightfoot, P.D., R.A. Cox, J.N. Crowley, M. Destriau, G.D. Hayman, M.E. Jenkin,
G.K. Moortgat, and F. Zabel, 1992: Organic peroxy radicals: Kinetics,
spectroscopy and tropospheric Chemistry, Atmos. Environm., 26A(10), 1,805-
1,961.
Liang, J., and D.J. Jacob, 1997: Effect of aqueous phase cloud chemistry on
tropospheric ozone, J. Geophys. Res., 102(D5), 5993-6001.
Logan, J.A., 1983: Nitrogen oxides in the troposphere: Global and regional budgets, J.
Geophys. Res., 88, 10,785-10,807.
Logan, J.A., 1985: Tropospheric Ozone: Seasonal Behavior, Trends, and
Anthropogenic Influence, J. Geophys. Res., 90(D6), 10,463-10,482.
Marenco, A., H. Gouget, P. Nedelec, J.-P. Pages, and F. Karcher, Evidence of a long-
term increase in tropospheric ozone from the Pic du Midi data series:
Consequences: Positive radiative forcing, J. Geophys. Res., 99, 16617-16632,
1994.
Milton M., P.T. Woods, B. Jollife, N. Swann and T. McIlveen, "Measurements of
toluene and other aromatic hydrocarbons by Differential-Absorption LIDAR in the
near-ultraviolet", Appl. Phys. B55, 41-45, 1992.
Papayannis A., G. Ancellet, J. Pelon, G. Megie, "Multiwavelength LIDAR for Ozone
Measurements in the Troposphere and the Lower Stratosphere", Applied Optics,
29, 467-476, 1990.
2008
115
Penkett, S.A., and K.A. Brice, 1986: The spring maximum in photo-oxidant in the
Northern hemisphere troposphere, Nature, 319, 655-657.
Penkett, S.A., 1988: Indications and causes of ozone increase in the troposphere, In
The changing atmosphere, edited by F.S. Rowland and I.S.A. Isaksen, J. Wiley and
Sons, p. 91.
Ridley, B.A., S. Madronich, R.B. Chatfield, J.G. Walega, R.E. Shetter, M.A. Carroll,
and D.D. Montzka, 1992: Measurements and model simulations of the
photostationary state during the Mauna Loa observatory photochemistry
experiment: Implications for radical concentrations and ozone production and loss
rates, J. Geophys. Res., 97(D10), 10375-10388.
Sillman, S., Tropospheric ozone and photochemical smog. in B. Sherwood Lollar, ed.,
Treatise on Geochemistry, Vol. 9: Environmental Geochemistry, Ch. 11, Elsevier,
2003.
Sillman, S., 1995: The use of NOy, H2O2, and HNO3 as indicators for ozone-NOx-
hydrocarbon sensitivity in urban locations, J. Geophys. Res., 100,(D7), 14,175-
14,188.
Sillman, S., J.A. Logan, and S.C. Wofsy, 1990: The sensitivity of ozone to nitrogen
oxides and hydrocarbons in regional ozone episodes, J. Geophys. Res., 95,(D2),
1837-1851.
Wayne, R.D., 1991: Chemistry of Atmospheres, Oxford Science publications, second
edition.
World Meteorological Organization (W.M.O.), 1994: Scientific assessment of ozone
depletion: 1994. Report No. 37.
WMO, The stratosphere - 1981: Theory and measurements, Global Ozone Research
and Monitoring Project, Report 11, WMO, Geneva, 1981.
2008
116
Zanis P., In-situ photochemical control of ozone at the Jungfraujoch in the Swiss
Alps. PhD thesis, School of Sciences, University of Bern, editor: Geographica
Bernensia, G59, ISBN 3-906151-34-4, pp. 126, 1999.
Zerefos C.S., K.A. Kourtidis, D. Melas, D. Balis, P. Zanis, L. Katsaros, H.T. Mantis,
C. Repapis, I. Isaksen, J. Sundet, J. Herman, P.K. Bhartia, and B. Calpini,
Photochemical Activity and Solar Ultraviolet Radiation (PAUR) Modulation
Factors: An overview of the project, Journal of Geophysical Research, 107(D18),
8134, doi:10.1029/2000JD000134, 2002.
2008
- 1: 43.6.2 (SO2)4.1.3 4.2 4.3 6: A 6.4 (NOx)
6.5 (SO2)6.7 6.9 Laser: Lidar1.2.2 , , . , , . , . , , 2 . , , . 2 , .
1.2.3 49% . , . , , , ( 1.1). . 60 , ) ) . 100 105 . , (600-1000 ). (1-2 ). . . 1.2.4
5.2 O3 NOx VOC 5.3 5..4
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