-

, 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

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, , ,

& , ,

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,

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, 1997: , ,

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, ,

, , , , 1984.

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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