1640.pdf

Ca rbo n_{y l} c o

m

_po u nds e xist in air, wate r, fo od, b iolog ic al f lui ds a nd tis s u e s, a sw el l a s

n o nb iolo_{g i}c al

m

ate rials.

M

a ny

m

ethods ha v e

b

e e n de v eloped to dete ct c a rbo ny lc o

m

po u nds in the

air,

i

n clu

d

ing n u

m

e r o u s de riv atizatio n r e age nts to

m

ake c a rbo ny l c om po u nds more stab le,

m

ulti p le

e x tr a ctio n

m

ethods, a s wel l a s

m

ultip le dete ctio n methods T he s e

m

ethods c a n be c o stl y a nd ti me

c o n s u

m

in_g, a nd als o

m

ake u s e of to x ic s olv e nts.

W

e s o ug ht a quick a nd in e x pe n siv e

m

ethod to dete ct

a n

d

_qu a nt

i f

_y tota

l

c a r

b

o n_y

l

s

i

n air s am p le s, spe c

i fi

c al

l

y

d

ie s el e x

h

a u st s a

m

p le s, a s w el l a s

e x tr a c el lula r

m

ed ia in b iolo_{g i}c al s a

m

_{p l}e s.

W

e

_d

e riv atiz ed sta nda rd c arbo n_{y l} c o

m

_po u nds w ith 2,4 -d i_ni_{tr o}

p he n_{y l h y d}r a zin e

₍

D N P H

₎

_;

he_pta n e

w

a s

m

o r e ef f icie nt t

h

a n _pe nta n e o r he x a n e in e x tr a ctio n of the de riv ativ e s a nd le a v e s e x c e s s

D N P H al

m

o st e ntir el y in the a_qu e o u s _{p h}a s e. To te st the u s efuln e s s of th is te chni qu e c a rbo ny ls fr o

m

1

^

d ie s el e xha u st we r e c ol le cte

d

o n Se_p-P_ak D N P H-S i l i_{c a c a r}t_ri

d

ge s, eluted, e x tr a cte

d

w it

h

hepta n e,

a n

d

a n alyz e

d

b y s_pe ctr o_{p h}otometr_y a nd H P L

C /

U V

/

M

S.

L in e a r r egr e s sio n a n al ysis ind ic ated a str o n_g c o r r elatio n

₍

0 9 8 2 1

₎

_betw e e n the U V abs o r

b

a n c e

(

3 6 5 n

m

)

of e a c

h

s a

_m

_{p l}e a n

d

the total

m

a s s o

f

c a rbo n_{y l d}e riv ativ e s s e_pa r ated b y H P L C a n

d

dete r

m

in ed

b

_y

M

S. T he u s efuln e s s o

f

th is te chniqu e wa s als o te sted o n a b iolog ic al s am p le. B E A S

-2 B c el ls we r e e x_po s ed to d i f fe rin_g c o n c e ntr atio n s of r e si du al oi l fl y a sh

(

R O F A

)

. U V a

b

s o rba n c e

in c r e a s ed w ith in c r e a sin_{g R O F A} c o n c e ntr atio n s, s ug ge sting that c a rbo ny l gr o ups

(

pr o

d

u cts of l

i

p i

d

pe r o xi datio n

₎

in c r e a s ed w ith in c r e a sin_g c o n c e ntr atio n s of R O F A. T he s e r e s u lts ind ic ate that a quick

a n

d i

n e x_pe n siv e

m

etho

d

to

d

ete ct a n

d

_qu a nti

_fy

total c a rbo n_{y l}s in air s a

m

_{p l}e s, spe ci fi c a

l

l y d ie s el

e xha u st s a

m

_{p l}e s, a s w el l a s e xtr a c el lula r

m

ed

i

a in

b

iolog ic al s a

m

p le s,

m

ay be a ch ie v e

d

thr o ug h the

e xtr a ctio n of c a rbo n_{y l d}e riv ativ e s w it

h

he_pta n e a nd s u

b

s e_qu e nt dete ct

i

o n b y s_pe ctr o_{p h}oto

m

etr_y. In

F

ir s

t, I

w

o u

l d l i k

e to tha nk

D

r .

M

ic

h

a el

M

a

d d

e n fo r c o o rd

in a

t

in

g t

h

e

f

o

l

lo

w i

ng pr o

j

e ct.

Dr.

M

a

d d

e n ta ug

h

t

m

e s o

m

u c

h m

o r e tha n

I h

a

d

e v e r a ntic

i p

ate

d l

e a r n

in

g

d

u r

i

ng t

h

e

l

a st t

w

o

ye a r s, a n

d w it

ho ut

h i

s pat

i

e n c e a n

d

e v e r

w i l l i

ngn e s s to

d i

s c u s s r e s e a r c

h d

e s

i

gn a n

d

te c

h

n

i

c a

l

is s

ue s, I

w

o u

l d

n ot

h

a v e

le a r n e

d

t

h

e c r

i

t

ic a

l

s

k i l l

s ne c e s s a r

y i

n c o

m p l

etin

g

s c

ie n

t

i fi

c r e s e a r c

h

.

I

a

m

a

l

s o _gr ate

f

u

l

to

D

r Lo u

is e

Ba

l l f

o r a

l w

a_ys e n c our a_g

i

n_g

m

e, a s

w

e

l l

a s a

l w

ays

b

r

in

g

i

n g a

s

m

i

l

e to

m

_{y f}a c e thr o u _g

h h

e r

m

a n _y sto rie s To

M

s L

is a

Da

i l

_y a n

d

M

r s. Jole e n So u

k

up, I a

m

e xtr eme

l

_y a_{p p}r e c

i

at

iv e

f

o r a

l l

o

f

t

h

e

ir e x

_pe rt

i

s e

in

h

e

l

_p

in

_g

m

e c o

m

_p

l

ete

m

_y r e s e a r c

h

e x_pe r

i m

e nts.

I a

ls o

o

w

e a

d

e

b

t o

f

_gr atitu

d

e to Dr .

W

i l l i

a

m

V

i

z u ete

f

o r s o

w i l l i

n g

l

y agr e e

i

ng to

b

e a r e a

d

e r o n

m

_y

m

a ste r s te c

h

n

i

c a

l

r e_po rt c o

m m i

t te e.

T o

m

_y

m

ot

h

e r,

Su s a n

,

m

y

b

r ot

h

e r s B J a n

d

M

a x , a n

d m

y s

i

ste r O

l i

v

i

a, tha n

k

yo u a

l l f

o r

yo u r c o n sta nt s u_{p p}o rt a n

d

u n c o n

d it

i

o n a

l l

o v e To

m

_y

f

at

h

e r, Lo u

i

s

(

d

e c e a s e

d

)

, t

h

a n

k

yo u

f

o r

T

A

B L E

O

F C

O N

T E N T S

Pa_ge

L I

ST

O

F

T A

B L E

S

v

i i

L I

ST

O

F F I

G

U R E

S

v

i i i

1

0

B A

C

K G R

O

U

N

D

9

L I

A

ir Pol lutio n 9

1.2 So u r c e s o

f A i

r Po

l l

utio n 1 1

1.3

C

a r

b

o ny

l

s

A

s a Co

m

po n e nt o

f A i

r Po

l lu

t

i

o n 1

3

1.

4 Ot

h

e r

S

o u r c e s o

f

Ca r

b

o n_{y l}s 2 1

1.5 He a

l

th E

f f

e cts o

f A l d

e

h

y

d

e s 2 2

1.5. 1

F

o r

m

a

l d

e

h

y

d

e 2 2

1

.5.

2

A

c r o

le

in

2

4

1.

5

.

3

A

c eta

l d

e

h

y

d

e 2

5

1.

5

4

Pr o

p

i

o n a

l d

e

h

y

d

e 2

6

1.5 5 Ac eto n e 2

6

1.5.6 Be n z al

d

e

h

y

d

e 2 7

1 6

M

et

h

o

d

s o

f

Dete ct

i

n_g

A i

r

b

o r n e A

l d

e

h

_y

d

e s 2 7

1.

6

1

R

e a

g

e nts

b

a s e

d

o n n itr o a r o

m

at

ic

h

y

d

r a z

in e s

2 7

1.6 2 1

-D i

m

_eth y l_a

m

i_{n o n a}

p hthale n -5-_{s u}

lf

_{o n}

y l d y dr a zi de 3 1

1

6 3

R

e a_ge nts

b

a s e

d

o n

b

e n z o o x a

d ia z o

le

s_tr u ctu r e s 3 1

1 6.

4

2

-

d

i p

h

_{e n}

y

la c e

ty

l

- l ,

3

-

i

_n

d

_{a n}

d io n e

-

l

-

h

y

d

r a z o n e

(

D

A

I H

)

3 3

1.

6

.

5

H

a

l

o

g

e n ate

d

a r o

m

at

i

c

h

y

d

r a z

i

n e r e age nts 3 4

1.

6

.

6

0

-A

l k

y

la

te

d h

_y

d

r o x _y

l

a

m i

n e s

34

2. 1

M

ate r

ia

l

s 3 8

2. 1. 1 B

i

o c

h

e

m i

c als a n

d

Re aga nts

3 8

2.1.2

Pa r

t

i

c

l

e

S

o u r c e a n

d C

o

l l

e ct

i

o n

3 8

2.1.3 A n al ytic a

l

a n

d

Expe r

i m

e nta

l

In str u

m

e nts 3 9

2

.

1 4

I

n V

i

tr o

E

xpo s u r e s

3 9

2

.

2

. Extr a ct

i

o n

So

lv e n

t V a

l i da

t

io n

4 0

2

.

3

En v

i

r o n

m

e nta

l

Sa

m

p

l

e Extr a ct

io n s a

n

d

An a

l

ys

i

s 4

3

2

.

4

B

i

o

l

og

ic a

l Sa

m

p

l

e Extr a ct

io

ns an

d A

n a

l

ys

i

s 4

5

3

.

0 R

E

SU

L T

S

4 7

3 1 Extr a ct

io n

o

f d i

n itr o_p

h

e n_y

l h

_y

d

r a z o n e s

b

_y

d

i

f f

e r e nt s o

lv e n

ts 4 7

3

.2 Extr a ct

io n

a n

d A

n a

l

ys

i

s o

f G

a s e o u s

D i

e s e

l

Ex

h

a u st

54

3.3 Extr a ctio n a nd

A

n al ysis of B iolog ic al s a

m

p le 6 4

4

.

0 D I SC U S SI

O N

A

N D C O N C

L

U S

I

O N S

6

7

5.

0 R E

F E R E

N C

E

S

7

6

A

_p

_p

e n

d i

x

A C h

e v r o n P

h i l l i

_ps

C h

e

m ic a

l C

o .

, Bo rge r, T

X

; 0 5 L

S C

e rt

i f

i c at

i

o n Fu e

l

, ty pe I

I

,

s u

l f

u r c o nte nt a_{p p}r o x

i m

ate

l

_y

3

4 7 p p

m

8 0

A p

p

e n

d i

x B : Ga s P

h

a s e a n

d

P

M

Pa r a

m

ete r s o

f D i

e s e

l

Ex

h

a u st a

f

te r 1:

3 0 d i

lutio n

w

ith

h

u

m i d

i

fi

e

d

a n

d

_pu r

i fi

e

d

a

i

r 8 1

A

_p

_p

e n

d i

x C :Ex_pe r

im

e nta

l

De s

i

_gn

f

o r

D i

e s e

l

Ex

h

a u st

Sa

m p l

e Extr a ct

io n s

8 2

A p

p

e n

d i

x D In

d i

v

i d

u a

l d i

n

i

tr o_p

h

e n_y

lh y d

r a z o n e

m

o

la r

c o ntr

i b

ut

i

on to

U V

a

b

s o r_{p t}

i

on

8 4

A

_{p p}e n

d i

x E: S pe ctr o_p

h

oto

m

etr

i

c

A b

s o r

b

a n c e

(

3 6 5 n

m

)

o

f

Se_p-P_ak D

N

P H -

Si l i

_{c a} C_{a r}t_ri

d

ge s

e x _po s e

d

to

d ie s e

l

e x

h

a u st 8 7

A p

p

e n

d i

x F: Tota

l

M

a s s o

f Ca r

b

o n_y

l

s

in

D

i

e s e

l

Ex

h

a u st

C

o

l l

e cte

d

o n

D N P H C

a rtr

i d

_ge s a n

d

A

_{p p}e nd ix G: Gr u

b b

s' Te st

f

o r Outl

i

e r s fo r Total Ca rbo n_{y l}

M

a s s 8 9

A

_p

_p

e n

d i

x

H

: Av e r a_ge c o n c e ntr at

io n

₍

n=

6

)

o

f

s_pe c

i f

i c c a r

b

o n_y

l

_gr o u_ps

f

o r

Se

_p-

P

_a

k

D

N

P

H

-

Si l i

_{c a}

Ca rtri

d

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d

to

d i

e s e

l

e x

h

aust

f

o r 2

h

our s a n

d b l

a n

k

, u ne xpo s e

d Se

p

-Pa

k

D

N

P

H

-

S i l i

c a

c a rtr

i d

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ft

e r s e_pa r at

i

o n

b

_{y H P L C},

d

ete ct

i

o n

b

y

M

S, a n

d

c o n c e ntr atio n

d

e r

i

v at

i

o n via sta n

d

a r

d

c u r v e s

f

o r s_pe c

i f

i c c ar

b

o n_y

l

s

9 0

A

_{p p}e n

d

ix I:

A

v e r a_ge _pe a

k

a r e a

(

n= 4

)

o

f

s_pe c

i f

i c c a r

b

o n_y

l

s a

ft

e r H P L C s e_pa r at

i

o n a n

d

M

S

L I

ST

O

F T

A

B L E

S

T a

b le

1.

3

. 1:

M

a

in

C

a r

b

o ny

l

Co

m

po u n

d

s, B y

C

o n c e ntr at

io n

, In

A m b ie n

t a n

d

In

d

o o r a

ir

2 0

T a

b l

e _{2 2 1 H P L C S y}ste

m G

r a

d i

e nt Pr o_gr a

m

4 2

Tab le 3 1. 1:

A

bs o rba n c e of a 3 X he x a n e e xtr a ctio n v e r s u s a 5

X

he x a n e e xtr a ctio n of a

m

ixtu r e of

d i

n

i

tr o_p

h

e n_y

l h

_y

d

r a z o n e s 4

8

T a

b le

3

.1.

2 U

V D ete ct

io

n o

f

D

N

P

H A ft

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n

W

it

h

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H

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T a

b le

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3

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m

pa r

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f U

n

d i l

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d A

E

0 0

0 4 3 Sta n

d

a r

d

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f

Pe nta n e v e r s u s Hepta n e

M

e a s u r e

d b

_y

M

S

5 2

T a

b le

3.1.4 In

d iv

i d

u a

l d i

n

it

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p

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2.1 Pe r c e nt o

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Fo r

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c eta

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l C

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6

0

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2 A i

r

b

o r n e

C

o n c e ntr at

i

o n

in

D i

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Ex

h

a u st

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a

m

b

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L I S T

O

F F I

G

U

R

E

S

F

i

_gu r e 1.3 1: C he

m

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l

Ex

h

a u st a n

d

Pr oport

i

o n o

f

C

h

e

m

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w i

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in

V o

l

at

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e

Or_ga nic Ga s P ha s e 14

F

i

_gu r e 1 6. 1.1 D e r

i

v atiz ation o

f

c a r

b

o n

y l gr ou_ps

w i

t

h

D

N

P H 2

8

F

i

_gu r e 1.6 1.2

M

o

le c u

la r s

tr u ctu r e o

f

n

i

tr o a r o

m

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i

c

h

y

d

r a z

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p N

P H a n

d

M

D

N

P H 2

8

F i gu r e 1.6.2.1 D

N

S H

m

ole c ula r str u ctu r e 3 1

F

i

_gu r e

1 6

.

3

.1

M

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la r

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f b

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b

a c

k b

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3 2

F i

_gu r e

1

.

6

.

4

.

1

M

o

l

e c u la r str u ctu r e of D

A

I H

3 3

F

i

_gu r e 1.

6

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M

o

l

e c u la r str u ctu r e o

f

T C P H a n

d

P F P H

3 4

F

i g

u r e

1

6.6. 1

M

ole c u la r

Str u c

tu r e o

f

P F B O

A

3

5

F i g

u r e

2

.2. 1

A

E 0 0 0 4 3 Sta n

d

a r

d C h

r o

m

ato

gr a

m

4 3

F i

_gu r e

3

.

1

.

1

:

A

v e r age pe r c e nt e x tr a ct

io n

b

y pe nta n e

,

h

e x a n e, o r

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p

ta n e o

f D N P H

o n

l

y s a

m p l

e s

b

a s e

d

o n

S

_pe ctr o_p

h

oto

m

etr

ic

A b

s o r

b

a n c e s 4

9

F

i

_gu r e 3 1.2

A

v e r age pe r c e nt e xtr a ct

i

o n

b

y Pe nta n e_, He x a n e_, o r H epta n e o f Un

d

i lute

d A

E 0 0 0 4 3

St

a n

d

a r

d Sa

m

_p

le s

b

a s e

d

o n

S

_pe ctr o_p

h

oto

m

etr

i

c

A b

s o r

b

a n c e s 5 0

F i gu r e 3.2. 1 S pe ctr o

p

h

oto

m

etric a

b

s o r

b

a n c e o

f i

n c r e a s

i

n_g

fr a c

t

io n s o

f d

ie s e

l

e x

h

a u st s a

m

_p

le s

.

5 5

F i

_gu r e 3.2 2 S pe ctr op hoto

m

etr

ic a

b

s o r

b

a n c e o

f i

n c r e a sing

f

r a ct

io n s o

f

d

ie s el e x ha u st s a

m

p le s.5 7

F i g

u r e

3

.

2 3

:

M

a s s o

f

c a r

b

o ny

l

s r e c o v e r e

d f

r o

m

s a

m

p

le

o

f d i

e s e

l

e x

h

a u st

59

F i

_gu r e

3

.

2

.4:

S

pe ctr op

h

oto

m

etr

i

c a

b

s o r

b

a n c e v e r s u s

m

a s s o

f

c a r

b

o ny

ls r e c o v e r e

d f

r o

m d i

e s e

l

e x

h

a u st

6 1

F i

_gu r e

3

.2.5: Av e r a

ge s_pe ctr o_p

h

oto

m

etr

i

c a

b

s o r

b

a n c e v e r s u s a v e r a_ge

m

a s s o

f

c a r

b

o n_y

ls

r e c o v e r e

d fr o

m d i

e s e

l

e x

h

a u st 6 3

F i gu r e 3 3 1 Av e r a

_g

e s

_p

e ctr o_p

h

oto

m

etr

i

c a

b

s o r

b

a n c e o

f

c e

l l

u

la r a n

d

e xtr a c el lula r

m

e

d

ia

6

5

C h

e a_pe r

M

etho

d

to

Q

u an t

i f

_{y T}ota_{l C}a r

b

o n _y

l

s

B y

La r s

D

. Pe r

l m

ut t

1

.

0

B

A C K G R O U

N D

1.1 A

i

r Pol lu t

io n

T

h

e

h i

sto r_y o

f

a

i

r _po

l l

ut

io n

a n

d i

ts

d

e

le

te r

i

o u s e

f f

e cts o n

h

u

m

a n s

i

s

w

e

l l

c

h

r o n

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c

l

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A

s

f

a r

b

a c

k

a s 1

3

0 6

K i

n _{g E}

d w

a r

d

state

d

"

b

e

i

t

k

no

w

n to a

l l w i

t

h i

n t

h

e s o u n

d

o

f

m

_y v o

i

c e_,

w h

o s o e v e r s

h

al l

b

e

f

o u n

d

_gu

i

lt_y o

f b

u r n

i

n_g c o al sha

l l

s u

f f

e r t

h

e

l

o s s o

f h i

s

h

e a

d

, "

thu s

b

a n n

in

_g

t

h

e u s e o

f

c o a

l

₍

H a z u c

h

a,

2 0 0 7

)

. T

h

e s e r

io u s c o n s e

qu e n c e s o

f

e x

po s u r e to

h i

_g

h l

e v e

ls o

f

a

m b i

e nt

a

ir

_po

l lu

t

i

o n

b

e c a

m

e e v

i d

e nt a s a r e s u

l

t o

f

s e v e r al

i

n c

i d

e nts

in

_t

_h

e 2

0

' c e ntu r_y. T he a r e a o

f

L

ie

_ge o n t

h

e R

i

v e r

M

e u s e

in

Be

l

_g

i

u

m w

a s o n c e o n e o

f

t

h

e

m

o st

h

e a v

i l

_y

in

d

u str

i

a

l i

z e

d

a r e a s o

f

E

u r o_pe,

w i

t

h

ste e

l m i l l

s, z

in

c s

m

e

l

te r s, g

l

a s s

m

a n u

f

a ctu r

i

ng

f

a cto r

i

e s, a s

w

e

l l

a s

f

e rt

i l i

z e r a n

d

e x _p

lo s

iv e s

_p

l

a nts Fr o

m

De c e

m b

e r 1 to De c e

m b

e r 5, 1 9 3 0, a t

h i

c

k f

og c o v e r e

d

t

h

e r eg

i

o n

Be_g

ir

m i

n _g o n De c e

m b

e r

3

,

19 3 0

,

h

u n

d

r e

d

s

b

ega n to e xpe r

i

e n c e r e sp

i

r ato ry sy

m

pto

m

s,

w i

t

h

o v e r

6 0 pe o_p

l

e

d

_y

in

_g t

h

e n e x t t

h

r e e

d

a_ys. T he c o

m

m

i

t te e r epo rt o n t

h i

s

f

og c o n c

lu

d

e

d

t

h

at

m

o r

b i d

ity

a nd

m

o rtal it_y

w

a s s o

le

l

_y

d

u e to r e s_p

ir a

to r_y tr a ct alte r atio n s

(

N

e

m

e r_y et a

l

, 2 0 0 0

)

.

A

ls o

d

eta

i l

e

d

f

o r t

h

e f ir st t

i m

e

is

the r o

l

e o

f

te

m

_pe r atu r e in v e r sio n a n

d f

o_g

in

a

ir

_po

l lu

t

io n

. It

w

a s c o n c

lu

d

e

d

t

h

at t

h

e

b

urn

i

n_g o

f

c o a

l

,

b

oth by

f

a cto r

i

e s an

d h

o u s e

h

o

l d

s

w

a s t

h

e

m

a

i

n

f

a cto r

i

n

m

o r

b i d i

ty an

d

m

o rta

l i

t_y

(

N e

m

e r_y et a

l

,

2 0 0 1

)

.

In _t

h

e

U

n

i

te

d

State s, t

h

e

fi

r st s e v e r e p

h

oto c

h

e

m i

c a

l

s

m

og ep

i

s o

d

e o c c u r r e

d i

n Lo s

e_{p i}s ode in that the e_{p i}s ode o c c ur re

d i

n t

h

e s u

m

m

e r, yet

w

a s st

i l l

inf lu e n c e

d b

y an

i

n v e r s

io n

laye r,

w

h ic

h

tr a_{p p}e

d

air _po

l l

uta nts at t

h

e s u r

f

a c e. T

h i

s in v e r s

i

o n

l

aye r, in c o

m

b in a

t

i

o n

w it

h lo

w

h

o r

i

z o nta

l

a

ir

m

o v e

m

e nt a n

d l

a c

k

o

f

tu r

b

u

l

e n c e, pr e v e nte

d

c o nta

m

in a nts

f

r o

m d

ispe r sing in t

h

e

u_{p p}e r atmo s_p

h

e r e. T

h

e pr

i

n c

i

pa

l h

e a

l

t

h

e

f f

e cts

f

r o

m

t

h

e s

m

og ep

i

s o

d

e

w

e r e te

m

po r a ry eye

i

r ritatio n,

w i

t

h

t

h

e s o u r c e s of ir ritat

io n

r epo rte

d

a s u nkn o

w

n at t

h

e t

i m

e

(

Se r

m

et a

l

, 1 9 4 8

)

.

P

e r

h

a

_p

s t

h

e

m

o st

f

a

m

o u s a

i

r

_p

o

l l

ut

io n

d i

s a ste r

i

s t

h

e

L

o n

d

o n Fo_g e

_{p i}

s o

d

e o

f

19 52

W

it

h

f

o_{g g y}

w

e at

h

e r, c o a

l

-

b

_{u r n}

in

g

h

o

m

e s_,

f

a cto r

i

e s a n

d

_po

w

e r _{p l}a nts, a

d

e n s e

f

og

la

i d

o v e r Lo n

d

o n

f

r o

m

D e c e

m b

e r 5, 1 9 52 to De c e

m b

e r

8

, 1 9 5 2

O f f

i c

i

a

l

go v e r n

m

e nt r epo rts

i

n

d i

c ate that t

h

e

f

o g

r e s u

l

te

d i

n a_{p p}r o x

i m

ate

l

_y

3 0 0 0 m

o r e

d

e at

h

s t

h

a n n o r

m

a

l d

u r

i

n _{g t}

h

e

f

i r st t

hr e e

w

e e

k

s o

f

De c e

m b

e r.

H

o

w

e v e r

, a r e a s s e s s

m

e nt o

f d

ata

b

y Be

l l

et a

l

(

2

0 0 1

)

i

n

d i

c ate s t

h

at a

b

o ut 12,

0 0

0

e x c e s s

d

e at

h

s o c c u r r e

d fr o

m D

e c e

m b

e r 1

9 5

2 to Fe

b

r u a r_{y 1}

9 5 3 d

u e to t

h

e a c ute, as

w

e

l l

a s

pe r s

i

st

in

_g e

f f

e cts

f

r o

m

t

h

e D e c e

m b

e r 1 9 5 2

f

o _g e_p

i

s o

d

e

M

o rta

l it

_y r ate s

f

r o

m

t

h i

s _pe r

i

o

d w

e r e

5 0-

3 00

%

h i

g

h

e r t

h

a n t

h

e _pr e v

io u s

_ye a r . Fu rt

h

e r, S O2

le v e

l

s

(

a v e r age c o n c e ntr atio n o

f

0.5 7 p p

m

)

w

e r e 1 9 t

i m

e s _gr e ate r t

h

a n c u r r e nt

U S N A A

_Q

S

sta n

d

a r

d

s

f

o r

S O

₂

₍

2 4-

hr

_{a v e r a}

ge

0 0 3

_{p p}

m

) (

Be

l l

et a

l

, 2 0 0 1

)

. F

i

n a

l l

y,

f

r o

m

De c e

m b

e r

3

to De c e

m b

e r 1

0

, t

h

e r e

la

t

iv e r

i

sk

f

o r

d

a

i l

y

m

o rta

l it

y a n

d

the _pr e v

i

o u s

d

a_y 's _po

l l

utio n

le v e

ls

w

a s

1

.

2 7 f

o r a

0

1 0

-p -p

m i

n c r e a s e

i

n t

h

e _pr e v

i

o u s

d

a_y's

SO

₂

l

e v e

l

.

T

ota

l

s u spe n

d

e

d m

at te r

(

T

S

M )

w

a s, at a v e r age c o n c e ntr at

io n s o

f 14

0 0 l

a

g

W

f

r o

m

De c e

m b

e r ₅-

8

, 1 9 5 2, a

l m

o st 1 0 t

i m

e s

h

i g

h

e r t

h

a n t

h

e c u r r e nt

U

.

S

.

N A A

Q

S

f

o r P

M

i o

(

1 5

0

^ g

W

)

(

U S E P A, 2 0 0 9

)

. Fo r a 1 0 0 \ig

lrx

i

in c r e a s e

in

T S

M

fr o

m

t

h

e

pr e v

i

o u s

d

a_y s, the a s s o c

ia

te

d

r e

l

ativ e r

i

s

k f

o r

m

o rta

l i

t y

w

a s

1

.

0 8

(

B

e

l l

et a

l

,

2 0 0

1

)

.

A i

r _po

l l

ut

i

o n r e

m

a

i

n s e x_pa n s

iv e

t

h

r o u _g

h

o ut t

h

e

w

o r

l d

_, r e_pr e s e nt

i

n_g o n e o

f

the

m

o st

w i d

e s_pr e a

d

r

is

k s to _po_pu

la

t

io n

he a

l

th. So

m

e air qu a

l i

ty pr o

j

e ct

io n s

h

a v e s

h

o

w

n t

h

at

in

m

a ny

r edu c ed si gni

fi c a

n t_{l y} o v er t

h

e n e x t 1 5 to

2 0

_ye ars

(

Cra

i

_g et a

l

, 2 0 0 8

)

. Ev e n in p la c e s

w

he r e air

qu a

l i

t_y sta n

d

a r

d

s a r e bein_g

m

et, e x te n siv e s c

i

e nti f ic data ind ic ate s a c o r r elatio n bet

w

e e n

b

oth

s

h

o rt-_{te r}

m

_{a n}

d l

_{o n} g-t

e r

m

e x

_p

o s u r e to a

m b i

e nt a

ir

_p

o

l l

ut

i

o n a n

d h

u

m

an

h

e a

lt

h

e

f f

e cts

(

Cr a

i

_g et

a

l

, 2 0

0 8

)

. T

h

e

W

o r

l d

He a

l

t

h O

rga n

i

z at

io n

e sti mate s that a

ir

po

l

lut

i

o n

i

s r e spo n s

i b l

e

f

o r 1.4

%

o

f

d

e aths

w

o rl

d w i d

e, a s

w

el l a s 0.8

%

o

f d

is a

b i l i

ty

-a

d

j

u ste

_d

l i fe _ye a r s

(W

_{H O}, 2 0 0 2

)

In a stud y b y

Co

h

e n et a

l

(

2 0

0

5

)

_, o ut

d

o o r

_p

a rtic u

la

te

m

atte r

(

P

M

)

a

ir

_po

l l

ut

io n

i

n u r

b

a n a r e a s

i

s e st

i m

ate

d

to

b

e r e s_po n s

i b l

e

f

o r a

_p

_pr o x

i m

ate

l

_{y 3}

%

o

f

a

d

u

l

t c a r

d io

_pu

l m

o n a r_y

d is e a s e

m

o rta

l i

t_y , 5% o

f

tr a c

h

e a,

b

r o n c

h

u s, a n

d l

u n g c a n c e r

m

o rta

l i

ty, a n

d

a

b

o ut

1%

o

f m

o rta

l i

t y

i

n c

h i l d

r e n a s a r e s u

l

t o

f

a c ute

r e s_p

i

r ato r_y

in

f

e ctio n . T

h

e s e

f

igu r e s a

m

o u nt to 0.8

0 m i l l i

o n pr e

m

atu r e

d

e at

h

s

(

1.

2

%

)

a n

d 6

.

4

m i l l i

o n

l

o st

l i f

e _ye a r s

(

0.5%

) (

Co

h

e n et a

l

, 2 0 0 5

)

.

1.2

S

o u r c e s of A ir Pol lu t io n

A

i

r _po

l l

uta nts c a n e

i

t

h

e r

b

e e

m i

t te

d d ir e c

t

l

_y

i

nto t

h

e at

m

o s_p

h

e r e

(p

r

i m

a r_{y p}o

l l

uta nts

)

o r

m

a_y

b

e

f

o r

m

e

d w i

t

h in

the at

m

o s

_{p h}

e r e

it

s e

l f

(

s e c o n

d

a r_{y p}o

l l

uta nts

)

. Po

l l

uta nts c a n

b

e

d

e

fi

n e

d b

y the

i

r

p h

ys

i

c a

l

state

(g

a s e o u s o r _pa rt

i

c u

la

te

m

at te r

)

_, a s

w

e

l l

a s

b

_{y t}

h

e

ir

_ge o

_g

r a_p

h i

c a

l

s c a

l

e

(p

o

i

nt,

l i

n e,

a r e a, a n

d

r e

gi

o n a

l

s o u r c e s

)

. Pr

i m

a ry po

l l

uta nts

in c

l

u

d

e s u

l f

u r

d io x

i d

e

(

S

O2

)

, o x

i d

e s o

f

n

i

tr oge n

(

N O

x

)

, c a r

b

o n

m

o n o x

i d

e

(

C O

)

, v o

l

ati le o rga n

i

c c o

m

po u n

d

s

(

V O C

)

, ca r

b

o n a c e o u s

p

a rt

ic

l

e s, a n

d

n o n

-c a r

b

o n a c e o u s _pa rt

ic

l

e s. Pa rtic u

l

ate

m

at te r

(

P

M )

i

s c

l

a s s

i fi

e

d b

y t

h

e

d i

a

m

ete r o

f

t

h

e pa rt

i

c

le

_,

a n

d

the E P A

h

a s sta n

d

a r

d

s

f

o r bot

h

P

M

j o

(

c o a r s e _pa rt

ic

l

e s

)

, pa rtic

l

e s

b

et

w

e e n 2.5 \i r a a n

d

1 0 [i

m

_,

a n

d

P

M

_{2 5}

(

fi

n e

_p

a rtic

le s

)

,

f

o r tho s e pa rticle s s

m

a

l l

e r t

h

a n 2.5 [j

m i

n

d

ia

m

ete r. U

l

tr a

f

i n e pa rt

ic

l

e s

(

P

M

0 2

)

a r e a

ls o

a pr

i m

a ry po

l l

uta nt pr e s e nt

i

n t

h

e at

m

o s

p h

e r e

(

U

S

E

P A

, 2 0

0 9

)

T

h

e o n

l

y

e ntir e

l

_y s e c o n

d

a r_y

_p

o

l l

uta n_t r e

_g

u

l

ate

d b

_y the

U S

E P

A N

at

i

o n a

l A m b i

e nt A

i

r

Q

u a

l i

t_y

St

a n

d

a r

d

s

i

s

or _ga n ic a e rosols, w h ich ar e ox i d iz ed organic co

m

p o u nds

fo r

m

ed via r eactio n s o

f

V O C

(

Ha r ris o n ,

2 0 0 6

₎

T

h

e

m

a

i

n s o u r c e o

f SO

2

i

s t

h

e c o

m b

u st

i

o n o

f f

u e

l

s o u r c e s c o nta

i

n

i

n_g s u

l f

u r,

l i k

e c o a

l

a n

d

o

i l

.

V

i

a c o

m b

u stio n, s u

l f

u r in the s o u r c e

i

s a

l m

o st c o n v e r ted

q

u a nt

i

tat

i

v el y to S O 2

(

H a r r

i

s o n et a

l

,

2 0 0 6

₎

. T he a

m

o u nt of s ul

f

u r in fo s si

l f

i i el v a rie s, a nd in

d

e v e

l

ope

d

c o u ntrie s,

m

o st is r e

m

o v e

d

f

r o

m m

oto r

f

u e

l

s

d

u r

i

n_{g t}

h

e r e

fi

n

i

n_{g p}r o c e s s. In Eu r ope

, t

h

e u s e o

f h

i g h s u

l f

u r c o a

l f

o r

p

o

w

e r

ge n e r at

i

o n a n

d

v e

h i

c

l

e

f

u e

l h

a s

d

e c

l

in e

d

a n

d

t

h

u s t

h

e

m

a

j

o r s o u r c e o

f S O

2 in t

h

e at

m

o s_p

h

e r e

h

a v e

d

e c

l i

n e

d

o v e r a

l l

₍

L

i

_p

m

a nn et a

l

, 2 0 0 6

)

. T

h

e a

d

v e nt o

f h i g h

c

h i m

n ey sta c

k

s

i

n

d

e v e

l

o

p

e

d

n at

i

o n s

h

a s a

l

s o

l

e

d

to

i

n c r e a s e s

i

n

S O

_{2 c o n c e n}tr at

i

o n s

i

n r u r a

l

a r e a s,

d

u e to tr a n spo rt,

w i

t

h

s o

m

e

r u r a

l

a r e a s

h

a v

i

n_{g h i g}

h

e r S O2 c o n c e ntr at

i

o n s t

h

a n u r

b

a n a r e a s. T

h

e u s e o

f h

i g

h

-_{s u} l f_{u r c o a}

l i

_n

d

e v e

l

o_p

i

n_g n at

i

o n s

i

s a ctu a

l l

_y o n t

h

e r

i

s e

f

o r _po

w

e r _pr o

d

u ct

i

on, a s

w

e

l l

a s

i

ts u s e

i

n

d

o

m

e st

i

c

c o o

k i

n _g, a n

d

e at

i

n

g

a n

d

a

m b i

e nt c o n c e ntr at

i

o n s o

f

S O2 the r e

f

o r e r e

m

a

i

n at

h i g h

c o n c e ntr at

i

o n s

(

L

i

_p

m

a nn, 2 0 0 6

)

. F

i

n a

l l

y, n atu r a

l

s o u r c e s o

f

S O2 e x

i

st, s u c

h

a s v o

l

c a n o e s.

A

s

w i

t

h

s ul

f

u r, t

h

e c o

m b

u stio n o

f f

u e

l

c on taining n itr o

g

e n c o n v e rts t

h

e n

i

tr oge n into o x

i d

e s

o

f

n

i

tr o _ge n. O i l a n

d

ga s c o ntain a

m

u c

h l

o

w

e r nitr oge n c o nte nt, s o c o a

l i

s t

h

e

m

a

i

n c ul prit in t

h

e

f

o r

m

at

i

o n o

f N O

_x . But,

N

Ox a r e a

l

s o

f

o r

m

e

d w h

e n at

m

o s

p h

e r

i

c n

i

tr oge n c o

m b i

n e s

w i

th o xy ge n

d

u r

i

n_g

h i

_g

h

-te

m p

e r atu r e c o

m b

u st

i

o n_,

w h i

c

h

o c c u r s

i

n a

l l h i

_g

h

-_te

m

pe r atu r e c o

m b

u st

i

o n

_p

r o c e s s e s

a n

d i

s t

h

u s a

h

u_ge r e a s o n r o a

d

tr a

f fi

c a n

d

_po

w

e r _ge n e r at

i

o n a r e t

h

e

m

a

j

o r s o u r c e s o

f N

Ox

(

Ha r ris o n et a

l

, 2 0 0 6

)

. On a g

l

o

b

a

l

s c a

l

e, ho

w

e v e r, n atu r al e

m

is sio n s o

f N O

x

f

a r o ut

w

e

i

g

h

a nt

h

r o_po_ge n

i

c s o u r c e s.

S

u c

h

s o u r c e s

i

n c

l

u

d

e v o

l

c a n

i

c a n

d b

a cte r

i

a

l

a ct

i

o n,

l i g h

tn

i

n g, a n

d

i

ntr u s

i

o n o

f

str ato s

_{p h}

e r

i

c n

i

tr o_ge n o x

i d

e s. T

h

e s e g

l

o

b

a

l

e

m i

s s

i

o n s, t

h

o ug

h

, a r e

d i

s

p

e r s e

d

t

h

r o u_g

h

o ut t

h

e Ea rth, a n

d

the r e

f

o r e

b

a c

k

gr o u n

d l

e v e

l

s o

f

N

O

x a r e r e

l

at

i

v e

l

y

l

o

w

(

Fo r a st

i

e r e et

Volatile o r_ganic c o

m

_po u nds

₍

V

O Cs

)

i

n clude a

w

i de r a n _ge of h_y

d

ro c arbo n s, o xyge n ate s,

halo_ge n ate s, a n d othe r c a rbo n c o ntainin g c o

m

po u n

d

s e x isting in the v apo r p

h

a s e in the

atmo s_p

h

e r e. V O Cs

, alo ng

w i

th N Ox, a r e t

h

e pr e c u r s o r s

i

n t

h

e c o

m

p

l

e x

f

o r

m

at

i

o n o

f

tr o

p

o sp

h

e r

i

c

o z o n e

A m

a

j

o r s o u r c e o

f

V O C s

i

n c

lu

d

e s the c o

m b

u st

i

o n o

f f

o s s

i l f

u e

l

s. T

h

e s e pr o c e s s e s

c o nta

i

n u n

b

u

m

e

d f

u el fr a_g

m

e nts

w h

ich a r e the n e

m i

t ted

i

n t

h

e

f

o r

m

o

f

V O C

(

Ha r ris o n et al ,

2

0

0

6

₎

.

1.3 Ca r

b

o ny ls

A

s a

C

o

m

po n e nt o

f A

ir Pol lut io n

T

h

e

m

a

j

o r

it

_y o

f

c a r

b

o n_y

l

s

(

i

.e. a

l d

e

h y d

e s a n

d k

eto n e s

)

, ty pe s o

f V O C

,

i

n t

h

e atmo sp

h

e r e a r e

c o n s

i d

e r e

d

s e c o n

d

a r_y a

ir

_p

o

l lu

ta nts

w i

t

h

t

h

e _pote nt

i

a

l f

o r

d

e

le

te r

i

o u s

h

u

m

a n

h

e a

l

th a n

d

e n vir o n

m

e ntal ef

f

e cts

O

the r c a r

b

o n_y

l

s t

h

at a r e n ot v o

l

at

i l

e a r e _pr

i m

a r

i l

_y at ta c

h

e

d

to _pa rt

i

c ulate

m

at te r.

A m

a

j

o r s o u r c e o

f

pr

i m

a ry c a r

b

o ny

l

s

in

t

h

e a

ir

is

t

h

e c o

m

b

u stio n o

f f

u e

l

. Co

m

b

u st

io n

o

f

f

u e

l i

s a n o x

i d

at

i

v e _pr o c e s s

in

w h i

c

h

a

l k

a n e s

(

s u c

h

a s t

h

o s e

f

o u n

d i

n

f

o s s

i l d ie s e

l

)

a r e o x

i d i

z e

d

to

a

l

c o

h

o

l

s, t

h

e n c a r

b

o ny

l

s, n e xt to c a r

b

o xy

l i

c a c

i d

s, t

h

e n e ste r s a n

d fi

n a

l l

y to c a r

b

o n

d i

o x

i d

e

(

G

u a r

ie

i

r o et a

l

,

2 0 0 8

)

H

o

w

e v e r, c o

m b

u st

io n

o

f f

o s s

i l f

u e

l

s

i

s n ot

10 0

%

e

f fi

c

i

e nt.

C

o n

d i

t

io n s

a r e

f

a v o r a

b l

e

f

o r

h

_y

d

r o x_y

l

at

i

o n o

f f

o s s

i l f

u e

l

s

w h

e n t

h

e

f

u e

l h

a s

b

e e n v a_po r

iz e

d

a n

d

a

d

e_qu ate

l

_y

m i

x e

d w it

h

a

i

r

b

e

f

o r e

b

e

in

_g

b

u r n e

d

. Ho

w

e v e r

,

w h

e n

b

u r n

i

ng c e a s e s, the o x

i d

at

io n

pr o c e s s

h

a

l

ts

at a n

i

nte r

m

e

d i

ate state,

l

e a v

in

g

b

y pr o

d

u cts s u c

h

a s a

l d

e

h

y

d

e s

(

Bo e r

la

ge et a

l

, 1 9 3 6

)

.

In

a

t_y

_{p i}

c a

l m

e

d iu

m

-

d

_ut

y

d i

e s e

l

tr u c

k

t

h

e

m

a

j

o r

i

t_y o

f b

_{y p}r o

d

u cts a s a r e s u

l

t o

f

c o

m b

u st

i

o n a r e _ga s

-p

h

a s e v o

la

t

i l

e o r_ga n

i

c s

(

5 8

.

7

%

)

b

y

w

e

i g h

t,

w h i l

e 1 4 7

%

a r e s e

m i

-_{v o}

l

_at

i le

g

a s

-p h

a s e u n r e s o

lv e

d

c o

m

_{p l}e x

m i

xtu r e

(

U C

M

)

, 1 1.

3

%

pa rt

ic

l

e

-p

h

a s e U C

M

, a n

d

1 5 2 %) e

l

e

m

e nta

l

c a r

b

o n O

f

the ga s

-p

h

a s e v olati le o r_ga n

ic s

(

F

i

_gu r e 1 3 1

)

, ap pr o xi

m

atel y 1 0.3

%

is fo r

m

al

d

e

h

y

d

e

, 1 9.

3

%

al ka n e s, 8.0

%

olefi n s

, and 6.5

%

a r o

m

atic s a nd cycl ic s

(

Scha u e r et al

, 1 9 9 9

)

. T he s e r e s ults a r e

ge n e r ate

d

fr o

m m

e

d i

u

m d

ut_y

d i

e s e

l

tr u c

k

s

d

r

i

v e n thr o u_{g h} the

h

ot-_{sta rt} F_ed_{e r a}l T _{e st} P_{r o c e}

d

_{u r e}

.

F

i

_gu r e

1

.

3

.1

C

he

m

ic al P ha s e s of D ie s el Ex ha u st a nd Pr opo r t io n of

C

he

m i

c als

w

i t h in

V

olat

i

le

O

r

_g

a n ic

G

a s P ha s e

(

S

cha u e r et al._, 1

9 9 9

)

%chem ic alpha s e fr om Medium-_Du

t y Die s el Tr u clt s

1 5 %

1 1 %

1 5 %

5 9 %

D ga s

-p ha s e v olat ile o r_ga nic s ■s e r ri-_{v olat lle}

ga s -p ha s UCM

D Pa rticle-_Pha s eUcm

Deleme ntalc a rbo n

%Volat ile Or_ga nic Ga s s e s

1 0 %

D al ka n e s ■ olef in s

□ a r omat ic s a nd cyclic s D fo rmaldeh y de ■ a c etal deh y de ■ pr opa n al ■ a c eto n e D c r oto n aldeh y de ■ ot he r c a rbo ny ls

It

i

s e v

i d

e nt t

h

at c a r

b

o n_y

l

s c o

m

_pris e a _{h i g h}

_p

e r c e nta_ge o

f

t

h

e _ga s

-p

h

a s e v o

l

at

i l

e o r_ga nic s.

W

ith r e_ga r

d

s to _pa rtic ulate o r_ga n

i

c c a r

b

o n e

m i

s s

i

o n s fr o

m h

e a v_y-

d

_ut

y

d

ie s el po

w

e r e

d

v e

h i

c

l

e s,

d

e_pe n

d i

n_g o n o_pe r at

i

n_g c o n

d i

t

i

o n s, t

h

e c a r

b

o n y

l f

r a ct

i

o n o

f

pa rt

i

c u

l

ate

m

at te r

i

s

m

e r e

l

y

3

.

3

-

3

.

9 %

(

De sta

i l l

ats et a

l

,

2 0 0 7

)

.

T h

e s e

d

ata,

h

o

w

e v e r ,

f

a

i l

to

i

n c

l

u

d

e t

h

e c o ntr

i b

ut

i

o n o

f f

o r

m

a

l d

e

h

y

d

e

a n

d

a c eta

l d

e

h

_y

d

e to _pa rt

i

c u

l

ate o r_ga n

i

c c a r

b

o n e

m i

s s

i

o n s.

J

a

k

o

b

e r et a

l

(

2 0 0 6

)

n ote s t

h

at

i

n

ge n e r al, e

m

is sio n s

f

a cto r s

f

o r c a r

b

o n y ls in t

h

e ga s p

h

a s e e x c e e

d

t

h

o s e o

f

t

h

e pa rt

i

c u

l

ate p

h

a s e,

a n

d f

o r t

h

o s e c o

m

_po u n

d

s t

h

at a r e o

b

s e r v e

d i

n

b

ot

h

_p

h

a s e s, ga s

-p

h

a s e e

m i

s s

i

o n s a r e at

l

e a st a

f

a cto r o

f

10 o r _gr e ate r t

h

a n t

h

o s e

f

o r t

h

e _pa rt

i

c u

l

ate _p

h

a s e.

S

e c o n

d

a r_y c a r

b

o n_y

l

c o

m

_po u n

d

s

i

n t

h

e at

m

o s_p

h

e r e a r e

f

o r

m

e

d

v

i

a t

h

e

f

o

l l

o

w i

n_g r e a ct

i

o n s

(

C

a r

l i

e r et a

/

_, 1

9 8 6

₎

:

(

1

₎

R + 0 2

^

R

0

2

(

2

₎

R O i- +

N

O- - ^

(

3

₎

R O

- + 0

2 - ^ Ca r

b

o n_{y l} c o

m

_po u n

d

+ H O2

T

h

u s, a ny o rga n

i

c r a

d i

c a

l

,

l i k

e h y

d

r o xy

l

r a

d i

c a

l

s

(

0

H

)

,

w i

t

h

t

h

e u npa

i

r e

d

e

l

e ctr o n o n a c a r

b

o n

ato

m

r e a cts

i

n t

h

e at

m

o s_p

h

e r e to

f

o r

m

c a r

b

o n_y

l

c o

m

_po u n

d

s.

A

l k

_y

l

₍

R O

N O

2

)

a n

d

_pe r o x_ya

l

k y l n

i

tr ate s

(

R O O

N

O2

)

a r e t

h

e r

m

al l y u n sta

b l

e, a n

d

c a n

t

h

e r e

f

o r e

b

e _p

h

oto

l

_yz e

d

, y

i

e

l d i

ng

m

o r e

f

r e e r a

d i

c a

l

s, a n

d

t

h

u s

m

o r e c a r

b

o ny

l

c o

m

po u n

d

s a r e

f

o r

m

e

d

v

i

a t

h

e

f

o

l l

o

w i

n

_g

r e a ct

i

o n s

(

C

a r

l i

e r et a

l

,

19 8 6

)

:

(

4

₎

R O

-+

N

O2 - ^ R

O N

O2

(

5

₎

R 0 2- +

N 0

2- - ^

R

O

O N

O2

A

t n

i

_g

h

t, n

i

tr

i

c o x

i d

e r a

d

ic al

(

N

O

-)

c o n c e ntr at

i

o n s a r e

l

o

w

, s o r e a ct

i

o n

(

2

)

d

o e s n ot o c c u r a n

d

R

O

2 r e a cts

m

a

i

n

l

_y v

i

a r e a ct

i

o n 5,

b

ut a

l

s o v

i

a t

h

e

f

o

l l

o

w i

ng r e a ct

i

o n s

(

C

a r

l i

e r et a

l

, 1

9 8 6

)

:

(

6

₎

R 0

2

-+ 0 3

^

R

O

- + 2

O

2

(

7

₎

R 1O 2 + R2O2

^

R iO - +

R2O +

O

2

(

8

₎

R

1

O

2 + R2O2 - ^ R 1- O-O-R 2 +

O

2

(

9

₎

R

1

O

2 + R2

O

2 - ^ a

l

c o

h

o

l

+ a

l d

e

h

y

d

e s +

O

2

In r e a ct

i

o n s 7-

9

, Ri a n

d R

2 r e

f

e r to

h

y

d

r o ge n o r o rga n

i

c gr o ups a n

d w h

e n Ri o r Ri equ als H, o n

l

y

r e a ct

i

o n

8

_pr o c e e

d

s.

W

h

e n t

h

e o rga n

i

c

g

r o up

h

a s a a -H

, r e a ct

i

o n 9

m

ay pr o c e e

d

(

C

a r

l i

e r et a

l

,

1

9 8

6

₎

.

Se c o n

d

a r_y c a r

b

o n_y

l

_gr o u_ps a r e

f

o r

m

e

d

at t

h

e _gr e ate st r ate

d

u r

i

n_g t

h

e

d

a_y,

w i

t

h

str o n

g

s u n

l i

_g

h

t, a n

d

t

h

e pr o

d

u ct

i

o n o

f

c a r

b

o ny

l

s

i

s

d

ete r

m

i

n e

d b

y t

h

e

f

o r

m

at

i

o n o

f f

r e e r a

d i

a

l

s, t

h

e

h

_y

d

r o x _y

l

r a

d i

c a

l

,

f

r o

m

o rga n

i

c c o

m

po u n

d

s

i

n t

h

e at

m

o sp

h

e r e. T

h

e s e r e a ct

i

o n s

d

epe n

d b

ot

h

o n

t

h

e c o n c e ntr at

i

o n o

f

t

h

e r e a ct

i

v e s_pe c

i

e s_,

l i k

e

h

_y

d

r o x _y

l

r a

d i

c a

l

s_, o z o n e

(

O

₃

₎

, a n

d

n

i

tr ate

(

N O

3

)

, a s

w

e

l l

a s t

h

e r ate c o n sta nts

b

et

w

e en t

h

e r e a ct

i

v e s_pe c

i

e s a n

d

o r_ga n

i

c c o

m p

o u n

d

s o

f

t

h

e tr o_po s_p

h

e r e

Car

b

o n_{y l} c o

m

_po u n

d

s a r e a

l

s o a cru cial c o

m

_po n e nt in the fo r

m

atio n o

f

tr o_po s_p

h

e r

i

c oz o n e.

C

a r

b

o n_y

l

s u n

d

e r_go _p

h

oto

l

_ys

i

s a n

d

r e a ct

w i

t

h

n

i

tr ate

(

N O

s

-)

a n

d h

_y

d

r o x_y

l

(

0 H

-)

r a

d i

c a

l

s.

Fo r

m

a

l d

e_{h y}

d

e

_{g i}

v e s

h

_y

d

r o x_y

l

r a

d i

c a

l

s v

i

a _p

h

oto

l

_ys

i

s. Fo r

m

al

d

e

h

y

d

e als o r e a cts

w i

t

h O

H

r ad ic a

l

s to _pr o

d

u c e H2O a n

d

a fo r

m

_y

l

r a

d i

c a

l

₍

H C O

₎

,

w h i

c

h

t

h

e n s u

b

s equ e nt

l

y r e a cts

w i

t

h

O2 to

f

o r

m

H O2 a n

d C O

(

Se

i

n

f

e

l d

et a

l

,

1

9 8 9

)

:

O H

+

_{H C H O}

- ^ _H

2

O

+ H

C O

-H

C O

-+

0

2

^

H

O

2+ C O

T

h i

s

i

s

i m

_po rta nt

i

n t

h

at H O 2,

i

n t

h

e pr e s e n c e o

f N O l

e a

d

s to

N O

2 a n

d O

H

(

S

e

i

n

f

e

l d

et a

l

,

1

9 8 9

₎

:

H

O

2 +

N O

^

N O

2 +

O

H

N O

2

i

s t

h

u s c r e ate

d w i

t

h

o ut u s

i

n_g up a

m

o

l

e c u

l

e o

f O

3, a n

d

t

h

u s e n a

b l i

ng

O

3 to a c c u

m

u

l

ate

i

n t

h

e

at

m

o s_p

h

e r e

N

O2 u n

d

e r_go e s _{p h}oto

l

_ys

i

s to _pr o

d

u c e

N O

_p

l

u s

O

a n

d

O3

i

s t

h

e n _pr o

d

u c e

d w h

e n t

h

e

O

H r a

d i

c a

l

s _pro

d

u c e

d

v

i

a t

h

e

d i

s s o c

i

at

i

o n o

f

a

l d

e

h

_y

d

e s at ta c

k

t

h

e

h

_y

d

r o c a r

b

o n s_,

f

o r

m i

n_g o r_ga n

i

c

pe r o x _y r a

d i

c a

l

s.

T h

e o r

ga nic _pe r o x_y r a

d i

c a

l

s,

i

n the pr e s e n c e o

f

O2 a n

d

s u n

l i

g

h

t

g

o o nto

f

o r

m

O 3

(

S

e

i

n

f

e

l d

et fl

/

,

19 8 9

)

.

N O

2 + /zv

^

N O

+

O

R

O

2 +

O

2 +

A

v

^

R

O

+

O

3

Ca r

b

o n_y

l

s

h

a v e

d i f f

e r e nt

d

e_gr a

d

at

i

o n r ate s

i

n t

h

e at

m

o s_p

h

e r e_, a s

w

e

l l

a s s e a s o n a

l

d i f f

e r e n c e s

i

n r ate s o

f d

e_gr a

d

at

i

o n

b

et

w

e e n s u

m

m

e r a n

d w i

nte r. Fo r

m

a

l d

e

h

y

d

e

i

s

_{p h}

oto-_{o x}

i d i

_{z e}

d

i

n s u n

l i

_g

h

t to c a r

b

o n

d i

o x

i d

e_, r e_pr e s e nt

i

n_g t

h

e

m

a

_j

o r

m

e c

h

a n

i

s

m i

n

w h i

c

h f

o r

m

a

l d

e

h

_y

d

e

i

s

r e

m

o v e

d f

r o

m

t

h

e at

m

o s_p

h

e r e.

T h

e a v e r age

h

a

l f

-

l i f

_{e o}

f

t

h i

_{s r e a c}t

i

_{o n}

i

_{s a}

p pr o x

_{i m}

ate

l

_y

5 0

m

in ute s

(

C O

M

E

A

P,

2 0 0 0

)

. P hoto c

h

e

m i

c a

l d

egr a

d

at

i

o n o

f f

o r

m

a

l d

e

h

y

d

e

, a n

d

ot

h

e r a

l d

e

h

y

d

e s,

(

C

O

M

E

A P

, 2 0 0 0

)

. It

h

a s

b

e e n e sti

m

ate

d b

y

A

E

A

T e chnolog y

(

1 9 9

9

)

t

h

at t

h

e

b

ou n

d

a ry

l

aye r

l i f

et

i m

e o

f f

o r

m

a

l d

e

h

_y

d

e

w

ith r e s_pe ct to r e

m

o v a

l b

_y

O

H r a

d

ic a

l

s in t

h

e

w i

nte r

i

s o n a v e r a_ge 6 2

d

a_ys a n

d i

n the s u

m m

e r 1 2

d

a_ys, a n

d

r e

m

o v a

l b

y

N

O3 r a

d i

c a

l

s

i

s o n a v e r age

80 d

ays T he

a v e r a_ge

b

o u n

d

a r_y

l

a_ye r

l i f

eti

m

e o

f

a c eta

l d

e_{h y}

d

e

w i

t

h

r e s_pe ct to r e

m

o v a

l b

_y r e a ct

i

o n

w i

th OH

r a

d

ic als

i

s, o n a v e r age,

3

.7

d

a

ys

in t

he

w i

nte r, a n

d

1 8

h

o u r s

i

n t

h

e s u

m m

e r, a n

d b

y r e a ct

i

o n

w

ith

N O

3 r a

d i

c a

l

s, o n a v e r age r e

m

o v a

l i

s

17 d

ays

(

A

E

A

T e c

h

no

l

og y,

19 9 9

)

R

e

m

o v a

l

o

f

f

o r

m

a

l d

e

h

_y

d

e a n

d

a c eta

l d

e

h

_y

d

e

i

n t

h

e

w i

nte r a v e r a_ge,

b y d i

r e ct p

h

oto

l

ys

i

s, 1

3 d

ays a n

d 6 7 d

ay s,

r e s_pe ct

i

v e

l

_y,

w h

i le the s u

m

m

e rt

i m

e a v e r age v

i

a

d i

r e ct p

h

oto

l

ys

i

s

f

o r

f

o r

m

a

l d

e

h

y

d

e

i

s 6 3

h

o u r s

a n

d

5.2

d

ays

f

o r a c eta

l d

eh y

d

e

(

A

E

A

Te chn o

l

og y

, 1 9 9

9

)

. T

h

e

l

a r

ge

d i f f

e r e n c e

b

etwe e n s u

m m

e r

a n

d w i

nte r r ate s

i

s

d

u e to t

h

e

f

a ct that

i

n t

h

e s u

m m

e r

m

o nt

h

s,

m

o r e

i

nte n s e p

h

oto r a

d i

at

i

o n a n

d

a

l

s o a s

h

_{i g h}e r te

m

_pe r atu r e s _pr o vi de the _pr o_pe r c o n

d

itio n s

f

o r t

h

e fa ste r

d

e_gr a

d

atio n of c

h

e

m

ic als.

Out

d

o o r s, the

m

o st a

b

u n

d

a nt c a r

b

o ny ls e xpr e s s e

d

a s pe r c e ntage s of L o s

A

ngele s c a r

b

o ny l air

c o nte nt c o

l l

e cte

d i

n 1 9 9

3 w

e r e

f

o r

m

a

l d

e

h

_y

d

e

(

2 4

%

)

, a c eta

l d

e

h

y

d

e

(

1

8

%

)

, a n

d

a c eto n e

(

7 %

)

(

G

r o s

_j

e a n et a

h

, 1

9 9 6

)

Othe r

m

a

i

n c a r

b

o ny ls in a

m b

ie nt a n

d

in

d

o o r a

i

r,

b

y c o n c e ntr atio n

i

n c

l

u

d

e a c r o

l

e

i

n,

p

r opa n a

l

, a n

d b

e n z a

l d

e

h

y

d

e

(

F

i

gu r e 1

3

1

)

.

Ge n e r a

l l

_y ,

i

n r e

m

ote, u npopu

l

ated r eg

i

o n s o

f

t

h

e

w

o r

l d

, a

m b i

e nt a

i

r c o n c e ntr at

i

o n s o

f

f

o r

m

a

l d

e

h

_y

d

e a r e

l

e s s t

h

a n 0.0 0 1

m

g

W

(

0.0 0

8

p p

m

) (

C

O

M

E

A

P

, 2 0 0

0

)

.

I

n popu

l

ate

d

a r e a s ,

t

h

o u_g

h

, c o n c e ntr at

i

o n s a r e u s u a

l l

y

i

n t

h

e r a n ge o

f 0

.

0 0 1

-

0

.

0 2 m

g

/m

^

(

0

.

0 0 8

-

0

.

0 16

p p

m

)

,

b

ut c a n

b

e a s

h i

_g

h

a s 0.0 1

m

g

W

(

0

.

0 8

p p

m

)

d

u r

i

ng pe r

i

o

d

s o

f h

e a vy tr a

f f

i c o r

d

u r

i

ng atmo sp

h

e r

i

c

i

n v e r s

i

o n _pe r

i

o

d

s

(

l

A

R

C

, 1

9 9 5

)

. In the o utdo o r e n v

i

r o n

m

e nt,

l

e v e

l

s o

f f

o r

m

a

l d

e

h

y

d

e a r e

h i

g

h

e st

i

n u r

b

a n a r e a s

d

u rin_g

h i

_g

h

te

m

_pe r atu r e atmo s_p

h

e r

i

c c o n

d it

i

o n s

w

ith lo

w w

in

d

a n

d

the r e

f

o r e,

l i

t t

l

e

m i

x

i

n_g. Fu rthe r, in a r e a s w ith h i g h c o n c e ntr atio n s o

f

v e

h i

c

l

e s

l

a c

k i

ng c atal yt

i

c c o n v e rte r s,