Quantitative Scanning Electron Microscopy Methods to Characterize Ambient Air PM2.

5
D. V. Martello, R. R. Anderson, C. M. White - NETL G. S. Casuccio, S. F. Schlaegle, - R. J. Lee Group, Inc.

donald.martello@netl.doe.gov

Different Missions
EPA Protect the public health DOE Assist the private sector in supplying

clean, abundant, and affordable energy

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PM2.5 Regulatory Process

1997 National Ambient Air Quality Standards

(NAAQS) for PM2.5 based on health effects

Mean annual concentration < 15 g/m3 Maximum concentration < 65g/ m3

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Why Is DOE Concerned About PM2.5?

Coal-based power systems contribute to PM2.5

Primary particles:

Ultra-fine fly-ash (Spherical Alumino-silicates,SAS), carbon soot

Gaseous precursors:

SO2, SO3, NOx React with NH3 in the atmosphere to form ammonium sulfate and ammonium nitrate particles

SIPs will likely restrict emissions from coal power plants.

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Ambient PM Monitoring and Characterization

Current Project Portfolio
Stuebenville Comprehensive Air Monitoring Project (SCAMP) NETL-PGH In-house Monitoring Station CMU/EPA Supersite Upper Ohio River Valley Project (UORVP)
Great Smoky Mountains Project (GSMP) Aerosol Research Inhalation Epidemiology Study (ARIES) Southeastern Aerosol Research and Characterization Program (SEARCH) Bravo Project

DOE-NETL Primary Funding

DOE-NETL Cost-sharing

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Regional Ambient PM Monitoring Sites

UORVP Sites
1 2

- Lawrenceville - Holbrook - Satellites

1 1

SCAMP Sites
- Primary - Satellites

- NETL In-house site

Coal-fired power plants

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Project Objective
Measure the degree that coal-fired utilities

contribute to the primary fine-particulate matter load in ambient air.

Experimental Approach
Use Spherical Alumino-Silicates (SAS) as the

measure of coal-fired utilities contribution to the primary fine-particulate matter load in ambient air.

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Experimental Objectives
Quantitatively validate the SEM methods. Assess comparability of polycarbonate filters to FRM teflon filters. Improve methods to account for most particle

species on the filters.

Identify particle species including SAS, sulfates, and carbonaceous.

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Secondary Electron Image

SAS Particle

Carbon-rich Particle

1 m

Sulfur Droplet
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Experimental Sample Collection

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Experimental Sample Collection

Andersen RAAS 400 Speciation Sampler Four flow channels One at 16.7 L/m, teflon filter for FRM comparison Two at 7 L/m, polycarbonate filters for SEM One at 16.7 L/m, quartz filter for EC/OC

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Experimental Sample Collection

Channel configurations 1: FRM teflon filter 2: Carbon denuder, Pd coated polycarbonate filter, Nylasorb filter 3: Carbon denuder, uncoated polycarbonate filter, Nylasorb filter 4: Carbon denuder, quartz filter, carbon filter

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Experimental Sample Collection

Pre-weigh and post-weigh filters. Sample SEM flow channels at 7 L/m found to

produce good particle dispersion at typical 15g/m3 ambient air loading.

Sample ambient air for 24 hours. Analyze SEM filters ASAP after sampling or

store particle filters under controlled conditions.

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Comparison of Gravimetric Filter Loading Variation: RAAS Polycarbonate versus FRM and RAAS Teflon versus FRM

Filter Type Polycarbonate Teflon

Number Avg. abs. of Filters difference,% 46 163 9.6 5.6

Standard Deviation 6.8 6.8

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Scanning Electron Microscopy (SEM)

SEM analysis can provide both morphology

and composition information for use in individual particle species determination.

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Scanning Electron Microscopy (SEM)

Image information Secondary Electron (SE): Morphology Backscattered Electron (BSE): Chemistry, Morphology Composition information X-ray (EDX/EDS): Chemistry

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Secondary Electron Image

SAS Particle

Carbon-rich Particle

1 m

Sulfur Droplet
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Backscattered Electron Image

SAS Particle

Carbon-rich Particle

1 m

Sulfur Droplet
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SEM Technique Validation

Test for uniform particle dispersion over the

filter surface.
Test for reasonable particle size distributions

within measured fields.

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Experimental SEM Analysis

Mount filters with double-sided silver tape; no filter post

sampling coating with carbon or metals

SEM conditions: 15kV; stable beam current; fixed WD SE image fields at 1000x; center to perimeter of filter

wedge analyzed; particle ID threshold monitored

Reference spectra used; 7 sec spectra acquisition Pd coated filters for carbon particle identification

C:Pd EDX ratio used for ID particle threshold

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Comparison of Filter Area required to Obtain 1000 Particle Images from filter Center and filter Perimeter

Section Location

Perim. of filter 0.0234 mm

2

Center of filter 0.0288 mm

2

Area Analyzed

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Comparison of Particle Species from filter Center and filter Perimeter, Excluding Ammonium Sulfate Blobs
Perim. Number % Particle Type SAS C-rich Crustal S-rich 1.8 85.5 8.6 4.1 Center Number % 1.4 79.6 14.4 4.6 Perim. Center Volume Volume % % 4.1 69.7 21.3 4.9 4.3 68.8 23.8 3.1

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Secondary Electron Images SAS

23KX

0.2 m

33KX

0.2 m

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Secondary Electron Images Carbon Chain Agglomerates

15KX

0.5 m

7500X

1 m

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Secondary Electron Images Crustal

16KX

0.5 m

22KX

0.2 m

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Secondary Electron Images Sulfur Deposits

15KX

0.5 m

27KX

0.2 m

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Secondary Electron Images Plant Material

19KX

0.2 m

22KX

0.2 m

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Distributions - Spherical Particles

All Quads, Aspect < 1.5, - 2198 Particles
400 350
# of Particles

All Quads, Aspect <1.5, Si>0, 948 Particles

250 200

300 250 200 150 100 50 0

0.20 0.44 0.68 0.92 1.16 1.40 1.64 1.88 2.12 2.36 2.60 2.84 3.08 3.32 3.56 3.80

# of Particles

150 100 50 0

0.20

0.45

0.69

0.94

1.18

1.43

1.67

1.92

2.16

2.41

2.65

2.90

3.14

3.39

3.63 1.40

Average Diameter, um

Average Diameter, um

All Quads, Aspect < 1.5, Si=0, S>0, 1065 Particles

300 250 200 150 100 50 0
0.20 0.39 0.59 0.78 0.97 1.16 1.36 1.55 1.74 1.94 2.13 2.32 2.51 2.71 2.90 3.09 3.28
# of Particles

All Quads, Aspect < 1.5, Si=0, S=0, 185 Particles

50 45 40 35 30 25 20 15 10 5 0
0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.50

# of Particles

Average Diameter, um

Average Diameter, um

From Quantitative Scanning Electron Microscopy of Ambient Air 2.5m Particles Using, Air Quality II Conference, McLean, Virginia, September 19-21, 2000.
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3.88

Non-spherical Particles
All Quads, Aspect >= 1.5, - 5081 Particles
1000 900 800 700 600 500 400 300 200 100 0

All Quads, Aspect >= 1.5, Si>0, 2166 Particles

600 500

# of Particles

# of Particles

400 300 200 100 0

0.20

0.53

0.85

1.18

1.51

1.84

2.16

2.49

2.82

3.14

3.47

3.80

4.12

4.45

4.78

0.20

0.50

0.81

1.11

1.41

1.71

2.02

2.32

2.62

2.93

3.23

3.53

3.83

4.14

4.44

Average Diameter, um

Average Diameter, um

All Quads, Aspect >= 1.5, Si=0, S>0, 2533 Particles

700 600

All Quads, Aspect >= 1.5, Si=0, S=0, 382 Particles

300 250

# of Particles

500 400 300 200 100 0

# of Particles

200 150 100 50 0

0.20

0.39

0.59

0.78

0.97

1.16

1.36

1.55

1.74

1.94

2.13

2.32

2.51

2.71

2.90

3.09

Average Diameter, um

Average Diameter, um

From Quantitative Scanning Electron Microscopy of Ambient Air 2.5m Particles Using, Air Quality II Conference, McLean, Virginia, September 19-21, 2000.
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3.28

0.20

0.56

0.91

1.27

1.62

1.98

2.33

2.69

3.04

3.40

3.75

4.11

4.46

4.74

Analysis Results FRM and SEM particle class data normalized to g/m3
Sample Start Date SEM SEM SEM Fe SEM 24 SEM SEM SEM All SEM SEM Hour Ammonium Carbon Crustal Spherical Crustal Ca/S Rich Metal Misc. FRM Sulfate Particles Particle AluminoRich Spheres Oxide Particles ug/m3 Types Silicates Particles 20.8 23.4 15.7 7.6 17.8 9.5 14.0 9.77 13.95 7.94 2.08 9.07 4.76 8.17 5.97 4.93 6.34 3.57 6.20 2.72 3.66 5.06 4.51 1.37 1.95 2.53 2.02 2.17 0.87 0.24 0.03 0.09 0.08 0.26 0.07 3.79 3.67 0.92 1.10 2.04 0.60 1.17 0.30 0.51 0.00 0.07 0.03 0.67 0.41 0.06 0.00 0.09 0.09 0.22 0.00 0.22 0.02 0.01 0.30 0.39 0.15 0.37 0.24 0.03 0.07 0.03 0.21 0.01 0.13 0.07

08/06/00 08/08/00 08/10/00 08/12/00 08/14/00 08/16/00 08/18/00

FRM and SEM particle class data normalized to g/m3 (SEM particle class volume fraction x daily FRM). SEM data normalized to IC ammonium sulfate analysis. From Quantitative Analysis of Ambient Air 2.5m Particles Using Scanning Electron Microscopy, 11th International Conference on Coal Science, San Francisco, Oct. 2001.

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R&P Carbon versus SEM Carbon

Carbon Values
8.000 7.000 6.000 5.000 4.000 3.000 2.000 1.000 0.000 0.00

CCSEM Carbon ug/m3

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

5.00

R&P 5400 Total Carbon ug/m3

From Quantitative Analysis of Ambient Air 2.5m Particles Using Scanning Electron Microscopy, 11th International Conference on Coal Science, San Francisco, Oct. 2001.

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Conclusions
SEM sampling methodology is reasonably

comparable to the FRM, based on ug/m3 filter loading.

The SEM technique provides satisfactory

results to continue the method development.

Although the methodology may be subject to

improvement, it is of sufficient quality to apply it to the comparative measurement of SAS particles in a more comprehensive study.
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Future Work
Correlate the SEM results with bulk analyses

of companion filters.
Analyze more filters to develop statistics on

distributional analysis of particle classes.

Use the palladium coating as an internal

standard for quantifying the particle species.

Revisit uncoated filters (check validity of

calculating carbon by difference).

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Acknowledgements
Dr. Elias J. George NETL Environmental

Safety and Health Division

Traci Lersch R.J. Lee Group The other PM2.5 Sampling and Analysis team

members
Mr. Thomas J. Feeley Product Manager:

Environmental and Water Resources, NETL

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