2008년 국내 배경지역 PM_(10) 및 PM_(2.5) 미세먼지의 화학 조성 분석

碩士學位論文

년 국내 배경지역

2008

PM

₁₀

및 PM

_2.5

미세먼지의 화학 조성 분석

濟州大學校 大學院

化 學 科

趙 銀 京

년 국내 배경지역

2008

PM

10

및 PM

2.5

미세먼지의 화학 조성 분석

指導敎授 姜 昌 禧

趙

銀

京

이

論文

을

理學 碩士學位 論文

으로

提出

함

2010

年

2

月

의

을

함

趙銀京

理學 碩士學位 論文

認准

_________________

審査委員長

_________________

委

員

_________________

委

員

印

印

印

Analysis of Chemical Compositions of PM

10

and PM

2.5

Fine Dust Particles Collected at

Background Area of Korea in 2008

Eun-Kyung Cho

(Supervised by professor Chang-Hee Kang)

A thesis submitted in partial fulfillment of the

requirement for the degree of Master of Science

2010. 2.

This thesis has been examined and approved.

DEPARTMENT OF CHEMISTRY

GRADUATE SCHOOL

μ

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측정소 설비 및 측정기기

1.

대기미세먼지 시료의 채취 및 분석

2.

μ

μ

μ

μ

μ

μ

μ

μ

μ

1. PM

10

과 PM

2.5

질량농도 측정

μ

μ

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μ

μ

μ

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0 20 40 60 80 100 120 140 9-Ja n 27-J an 8-Fe b 20-F eb 3-M ar 9-M ar 15-M ar 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 20-A pr 26-A pr 2-M ay 8-M ay 14-M ay 4-Ju n 16-J un 10-J ul 28-J ul 27-A ug 14-S ep 26-S ep 20-O ct 1-No v 13-N ov 25-N ov 7-De c 19-D ec 31-D ec M as s C on ce nt ra ti on (μ g/ m 3 ) PM10 PM2.5

μ

μ

0 20 40 60 80 100 120 140 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 20-A pr 26-A pr 2-M ay 8-M ay 14-M ay 4-Ju n 16-J un 10-J ul 28-J ul 27-A ug 14-S ep 26-S ep 20-O ct 1-No v 13-N ov 25-N ov 7-De c 19-D ec 31-D ec M as s C on ce nt ra ti on (μ g/ m 3) PM10

y = 0.6714x + 8.4831

R

2

= 0.6597 (r=0.812)

0

50

100

150

0

50

100

150

PM

10

(µg/m

3

)

G

os

an

O

b

se

rv

at

io

n

N

et

w

or

k

(

µ

g/

m

3

)

분석 데이터의 이온 수지 비교

2.

y = 0.9876x + 1.3745

R

2

_{= 0.965 (r=0.982)}

0

200

400

600

0

200

400

600

Σ[Cation]

eq

Σ

[A

n

io

n

]

eq

y = 0.9361x + 0.4272

R

2

= 0.9817 (r=0.991)

0

200

400

600

800

0

200

400

600

800

Σ[Cation]

eq

Σ

[A

ni

on

]

eq

3. PM

10

과 PM

2.5

미세먼지 분석 결과

μ

μ

μ

μ

μ

μ

0 8 16 24 32 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 26-A pr 2-M ay 8-M ay 17-M ay 10-J un 22-J un 16-J ul 3-Au g 8-Se p 20-S ep 2-Oc t 26-O ct 7-No v 19-N ov 1-De c 13-D ec 25-D ec C on ce nt ra ti on (μ g/ m 3) NH4+ NO3- nss-SO42-0.0 0.5 1.0 1.5 2.0 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 26-A pr 2-M ay 8-M ay 17-M ay 10-J un 22-J un 16-J ul 3-Au g 8-Se p 20-S ep 2-Oc t 26-O ct 7-No v 19-N ov 1-De c 13-D ec 25-D ec C on ce nt ra ti on (μ g/ m 3) K+ Mg2+ nss-Ca2+ 0.12 0.18 ce n tr at io n (μ g/ m 3 ) _1.2 1.8 - C on ce n tr at io n (μ g/ m 3) H+ F-HCOO- CH3SO3-

CH3COO-0 5 10 15 NH 4+ _Na+ K+ Mg2 + NO 3- _C l-HC O 3-ns s-Ca2+ ns s-SO42 -C on ce n tr at io n (μ g/ m 3 ) 0.0 0.3 0.6 0.9 H+ F-HC OO -CH 3CO O -CH 3SO 3-C on ce nt ra ti on (μ g/ m 3 ) H+ 0.1% NH4+ 11.7% Na+ 10.5% K+ 1.8% Mg2+ 1.5% NO3 -16.6% Cl -13.8% HCO3 -4.8% nss-Ca2+ 2.4% nss-SO4 2-34.7% F -0.2% HCOO -0.2% CH3COO -1.4% CH3SO3 -0.2%

0 1 2 3 4 5 S Al Fe Ca Na K Mg C on ce n tr at io n (μ g/ m 3 )

0

60

120

180

Ti

Mn

Ba

Sr

Zn

V

Pb

Cr

Cu

Ni

Co

Mo

Cd

C

on

ce

n

tr

at

io

n

(n

g/

m

3

)

Cd 0.0% Mo 0.0% Co 0.0% Ni 0.3% Cu 0.1% Cr 0.3% Pb 0.3% V 0.1% Zn 1.2% Sr 0.1% Ba 0.1% _Mn 0.2% Ti 0.3% S 35.3% Mg 4.7% _K 5.3% Na 22.3% Ca 11.2% Fe 6.5% Al 11.7%

μ

μ

μ

0 8 16 24 32 9-Ja n 27-J an 8-Fe b 20-F eb 3-M ar 9-M ar 15-M ar 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 20-A pr 26-A pr 2-M ay 17-M ay 10-J un 22-J un 16-J ul 3-Au g 8-Se p 20-S ep 2-O ct 26-O ct 7-No v 19-N ov 1-De c 13-D ec 25-D ec C on ce n tr at io n (μ g/ m 3) NH4+ NO3- nss-SO42-0.0 0.5 1.0 1.5 2.0 9-Ja n 27-J an 8-Fe b 20-F eb 3-M ar 9-M ar 15-M ar 21-M ar 27-M ar 2-Ap r 8-Ap r 14-A pr 20-A pr 26-A pr 2-M ay 17-M ay 10-J un 22-J un 16-J ul 3-Au g 8-Se p 20-S ep 2-Oc t 26-O ct 7-No v 19-N ov 1-De c 13-D ec 25-D ec C on ce n tr at io n( μg /m 3) K+ Mg2+ nss-Ca2+ 0.2 0.3 0.4 at io n( μg /m 3) _0.6 0.9 n tr at io n( μg /m 3 ) H+ F-HCOO- CH3SO3-

CH3COO-0 5 10 15 NH 4+ _Na+ K+ Mg2 + NO 3- _C l-HC O 3-ns s-Ca2 + ns s-SO42 -C on ce n tr at io n( μg /m 3) 0.0 0.1 0.2 0.3 0.4 H+ F-HC OO -CH 3CO O -CH 3SO 3-C on ce nt ra tio n( μg /m 3) F -0.2% HCOO -0.4% _H+ 0.1% CH3COO -1.0% CH3SO3 -0.2% Na+ 3.2% K+ 2.6% Mg2+ 0.9% Cl -2.1% HCO3 -2.1% nss-Ca2+ 2.3% NO3 -14.7% NH4+ 18.7% nss-SO4 2-51.4%

0.3 0.6 0.9 1.2 1.5 P M2. 5 /P M10 r at io

월별 농도 변화

4.

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0 5 10 15 20 25 30 35 Dec Nov Oct Sep Aug Jul Jun May Apr Mar Concentration(μg/m3) NH4+ Na+ K+ Mg2+ NO3- Cl- HCO3-nss-Ca2+ nss-SO42-Nov Oct Sep Aug Jul Jun May Apr Mar H+ F- HCOO- CH3COO-

CH3SO3-0 5 10 15 20 Dec Nov Oct Sep Aug Jul Jun May Apr Mar Feb Jan Concentration(μg/m3₎ NH4+ Na+ K+ Mg2+ NO3- Cl- HCO3-nss-Ca2+ nss-SO42-0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 Dec Nov Oct Sep Aug Jul Jun May Apr Mar Feb Jan Concentration(μg/m3) H+ F- HCOO- CH3COO-

CH3SO3-μ

μ

μ

μ

0 3 6 9 12 D ec Nov O ct Se p Aug Jul Jun M ay Apr M ar C once ntration(μg/m3₎ Al F e Ca Na K M g S 0 20 40 60 80 D ec Nov O c t Se p Aug Jul Jun M ay Apr M ar C once ntration(ng/m3₎ V C u N i Co M o Cd Aug J ul J un M ay Apr M ar Ti M n Ba S r Zn V P b

안개 박무 연무 시의 농도 비교

5.

,

,

0 8 16 24 32

NH4+ Na+ K+ Mg2+ NO3- Cl- HCO3- nss-Ca2+

nss-SO42-C on ce nt ra ti on (μ g/ m 3 ) 0 1 2 3 4 5 F og & M is t / N on -E ve nt , H az e / N on -E ve n t ra tio Non-Event Fog & Mist Haze

Fog & Mist / Non-Event ratio Haze / Non-Event ratio

0.0 0.3 0.6 0.9

H+ F- HCOO- CH3COO-

CH3SO3-C on ce nt ra ti on (μ g/ m 3 ) 0 1 2 3 4 5 F og & M is t / N on -E ve n t, H az e / N on -E ve nt r at io Non-Event Fog & Mist Haze

Fog & Mist / Non-Event ratio Haze / Non-Event ratio

0 8 16 24

NH4+ Na+ K+ Mg2+ NO3- Cl- HCO3- nss-Ca2+

nss-SO42-C on ce nt ra ti on (μ g/ m 3 ) 0 1 2 3 4 5 F og & M is t / N on -E ve n t, H az e / N on -E ve n t ra ti o Non-Event Fog & Mist Haze

Fog & Mist / Non-Event ratio Haze / Non-Event ratio

0.1 0.2 0.3 C on ce nt ra ti on (μ g/ m 3 ) 1 2 3 4 5 og & M is t / N on -E ve n t, H az e / N on -E ve nt r at io Non-Event Fog & Mist Haze

Fog & Mist / Non-Event ratio Haze / Non-Event ratio

0 4 8 1 2 Al F e C a N a K M g S C on ce nt ra ti on (μ g/ m 3) 0 1 2 3 4 5 F og & M is t / N on -E ve n t, H az e / N on -E ve nt r at io N o n- E ve n t F o g & M i s t H a ze F o g & M i s t / N o n- E ve nt r a ti o H a ze / N o n- E ve nt r a t i o 0 9 0 1 8 0 2 7 0 T i M n B a S r Z n V P b C on ce nt ra ti on (n g /m 3) 0 1 2 3 4 5 F og & M is t / N on -E ve n t, H az e / N on -E ve n t ra ti o N o n - E v e n t F o g & M i s t H a ze F o g & M i s t / N o n - E v e n t r a t i o H a ze / N o n - E v e n t r a t i o 0 1 0 2 0 3 0 4 0 5 0 C r C u N i C o M o C d C o nc en tr at io n( n g/ m 3) 0 1 2 3 4 5 F og & M is t / N on -E ve n t, H az e / N on -E ve n t r at io N o n - E v e n t F o g & M i s t H a ze F o g & M i s t / N o n - E ve n t r at i o H a ze / N o n - E v e n t r a t i o

산성화와 중화 특성

6.

μ

μ

μ

μ

y = 1.0653x - 0.0125 R2 _{= 0.949 (r=0.974)} 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 Sum([H+_]+[NH 4+]+[nss-Ca2+]+[K+]+[Mg2+]) S um ([ N O 3 -]+ [n ss -S O 4 2 -]+ [F -]+ [H C O O -] + [C H 3 C O O -]+ [C H 3 S O 3 -]) PM10 y = 0.9211x + 0.011 R2 = 0.9545 (r=0.977) 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 Sum([H+_]+[NH 4+]+[nss-Ca2+]+[K+]+[Mg2+]) Su m ([ N O 3 -]+ [n ss -S O 4 2 -]+ [F -]+ [H C O O -] + [C H 3 C O O -]+ [C H 3 SO 3 -]) PM2.5

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­

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대기 에어로졸의 발생기원

7.

1

10

100

1000

E

F

Se a w at er

0

1

10

100

1000

K+

Ca2+

M g 2+

SO42-

Cl

-E

F

Se aw a te r

0 1 10 100 1000 Fe Ca Na K Mg Ti Mn Zn Vl Pb Cu Ni Co Cd E F C ru st a l

대기오염물질의 유입 경로

8.

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10

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30

40

50

60

90

100

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150

Longitude(°E)

L

at

it

ud

e(

°N

)

SectorⅠ (South China) SectorⅡ (North China) SectorⅢ (Korean Peninsula) SectorⅣ (East Sea & Japan)

SectorⅤ (North Pacific Ocean)

Ⅲ Sector

18.2%

Ⅴ Sector

2.3%

Ⅱ Sector

40.9%

etc

15.9%

Ⅰ Sector

9.1%

Ⅳ Sector

13.6%

10

20

30

40

50

60

90

100

110

120

130

140

150

Longitude(°E)

L

at

it

ud

e(

°N

)

SectorⅠ (South China) SectorⅡ (North China) SectorⅢ (Korean Peninsula) SectorⅣ (East Sea & Japan)

SectorⅤ (North P acific Ocean)

Ⅳ Sector

13.8%

Ⅰ Sector

6.9%

etc

10.3%

Ⅱ Sector

53.4%

Ⅴ Sector

1.7%

10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 L at it u de (° N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 L at it ud e( °N )

10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it u de (° N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N )

10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N )

10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N )

10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it u de (° N ) 10 20 30 40 50 60 90 100 110 120 130 140 150 Longitude(°E) L at it ud e( °N )