Fine Particle Characterisation and Source Apportionment in Manila

and Hanoi from 2001-2005 Using Nuclear

TechniquesDavid CohenANSTO, Australia

This talk will discuss:-

Ion Beam Techniques- what are they?

PMF methods for source apportionment

Fine particle (PM2.5) masses/ sources in Manila and Hanoi during 2001-05.

Further info can be found at our WEB site

http://www.ansto.gov.au/nugeo/iba/

Nuclear Method for Fine Particle Characterisation

Incident Ion Beam

Sputtered Atoms

X - RaysChannelled Ions

Light, UV

Scattered Ions

b ± Decay

Sample

Reaction Productsg - RaysProtonsNeutronsIons

Electrons

Recoiled

Backscattered Ions

What is Ion Beam Analysis (IBA)

Pass relativistic protons from accelerators through filters

Nuclear Interactions;

g-rays

Scattering

Recoil ….

Atomic Interactions;

X-rays

Channelling

Electrons….

STAR 2MV Tandetron ANSTO

PIGE

100

1,000

10,000

100,000

0 200 400 600

Energy (keV)

Cou

nts

/3 µ

C

511 keV

F 197 keV

Na 440 keV

(21±2) µg/cm2

PESA

1

10

100

1,000

10,000

0 1000 2000 3000

Energy (keV)

Cou

nts

/ 3 µ

C

H

5.4 µg/cm2

C,F

2.6 MeV protons

RBS

0

200

400

600

800

1000

0 1000 2000 3000

Energy (keV)

Cou

nts

/ 3 µ

C

O

C

F

2.6 MeV protons

Four techniques cover most of the periodic table from H to U

PIXE

1

10

100

1,000

10,000

100,000

0 2 4 6 8 10 12 14 16

X-ray Energy (keV)

Co

un

ts/

3µ

C

Data

Bkg

Fit

S

Fe

Zn

Cl

KCa

Ti

Cu

Si

Al

PbLb

Mn

PbLa

Rb

Br

Pb=994 ng/m3

Accelerator Based Analyses

Basic advantages include:

High sensitivity (count individual atoms) Analyse small samples (pg) in few minutes Multi-elemental – H to Pb in one

measurement Non-destructive so can use other

techniques

100µg samples on air filters are ideally suited to these methods.

How to collect samples?

Cyclone and Stacked filter samplers at Hong Kong

Stacked filter heads

Stacked filter cassette

Clean and exposed filters

2.6MeV proton beam spot

Asian PM2.5 Sampling Sites (2001-2005)

Hong Kong

Cheju Is.

Manila

Hanoi

Sado Is.

Hong Kong

Dust

S

Dust Out of China in 2002

Manila

0

50100

150

200250

300

1/01

/200

1

1/07

/200

1

1/01

/200

2

1/07

/200

2

1/01

/200

3

1/07

/200

3

1/01

/200

4

1/07

/200

4

1/01

/200

5

1/07

/200

5

Mas

s (µ

g/m

3 )

Hanoi

0

50

100

150

200

250

1/01

/200

1

1/07

/200

1

1/01

/200

2

1/07

/200

2

1/01

/200

3

1/07

/200

3

1/01

/200

4

1/07

/200

4

1/01

/200

5

1/07

/200

5

Mas

s (µ

g/m

3 )

Fine Particle Mass PM2.5 at Manila and Hanoi 2001-05

US EPA PM2.5 annual goal 15µg/m3, 24hr goal 65µg/m3

Australia PM2.5 annual goal 8µg/m3, 24hr goal 25µm3

Av.=(46±20)µg/m3, max=260µg/m3 Av.=(54±34)µg/m3, max=222µg/m3

New Year

Positive Matrix Factorisation (PMF)

Recent source apportionment techniques provide powerful one step methods to determine source fingerprints and their contributions to the measured mass

Sources (Fij) and their contributions (Gjk)

calculated directly from the original input data

matrix (Mjk).Mik = Fij * Gjk + err

= *

H to Pb

1 to

100

H to Pb

1 to

7

1 to

100

1 to 7

Typical Source Fingerprints Fij using IBA and PMF

Wind Blown Soil

Secondary Sulfur

Diesel/ Oil burning

Black carbon, soot

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Soil

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n 2ndryS

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Diesel/Oil

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Soot

Typical Source Fingerprints using IBA and PMF

Coal burning (Sea)Ca based Industry

AutomobilesSmoke, biomass burning

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Smoke

PMF210) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Auto3

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n IndCa

PMF2(10) PM2.5 Sources Hanoi 2001-06

0.000

0.001

0.010

0.100

1.000

H Na Al

Si P S Cl

K Ca Ti V Cr

Mn Fe

Co

Ni

Cu

Zn

Br

Pb

BC

Sou

rce

Fra

ctio

n Coal

Site %Sea %2ndryS

%Auto,Ind,Diesel,

Soot

%Soil %Smoke

Manila 7 Factors

1.1±2.2%

20±11%

60±13% 2.6±2%

17±11%

Hanoi 10 Factors

- 21±10%

58±13% 9.0±5%

12±6%

Mean Percentage Source Contributions

at Manila and Hanoi 2001-2005

Hanoi

0

4,000

8,000

12,000

16,000

1/04

/200

1

1/10

/200

1

1/04

/200

2

1/10

/200

2

1/04

/200

3

1/10

/200

3

1/04

/200

4

1/10

/200

4

1/04

/200

5

1/10

/200

5

S (

ng/

m3 )

Hanoi 30 Apr 03, 10 Oct 044 Day Back Trajectories (every 4hr)

10

15

20

25

30

35

40

45

50

90 95 100 105 110 115 120 125 130 135 140

Longitude

La

titu

de

Sites

300m

500m

Beijing

UlaanBaatar

Cheju Is.

Sado Is.

Hong Kong

Manila

Hanoi

10Oct04

30Apr03

Hanoi

05

1015202530

1/04

/200

1

1/10

/200

1

1/04

/200

2

1/10

/200

2

1/04

/200

3

1/10

/200

3

1/04

/200

4

1/10

/200

4

1/04

/200

5

1/10

/200

5

Soi

l (µ

g/m

3 )

Soil-Sulfate Transport to Hanoi

HYSPLIT 4 day back trajectories calculated every

4 hours

Manila PM2.5 1Jan01-26Dec04

0

2

4

6

8

10

12

14

0 500 1000 1500

Days after 1 Jan 01

Su

lfu

r (µ

g/m

3 ) 1 Jan Fireworks

13Oct04Oct03

Long Range Transport of Fine Sulfates

HYSPLIT 5 day back trajectories every 4 hours for 12 to 14 Oct 04 show high sulfur measured on 13 Oct 04 at Manila may originate from long range transport from South Korea. Similar long range patterns were observed for October of 2003.

Manila 12-14 Oct 045 Day Back Trajectories (every 4hr)

10

20

30

40

50

100 110 120 130 140 150

Longitude

Lat

itu

de

Sites

300m

500m

BeijingUlaanBaatar

Cheju Is.

Sado Is.

Hong Kong

Manila

Hanoi

Summary

Accelerator based IBA techniques, in particular, are ideal for generating large data sets containing many elements needed for characterisation and source modeling of air pollution.

20-40 elements are not uncommon. The larger the number of elements the better the sources are characterised.

Generally nuclear analytical methods are accurate, precise, fast and non destructive on microgram-picogram samples.

In many cases this is the only way this data can be obtained!

Acknowledgements

Our collaborators; Vuong Thu Bac at Institute of Nuclear

Sciences and Technology, Hanoi, and

Flora Santos at Philippines for Nuclear Research Institute, Manila

All the IBA accelerator staff at ANSTO