Causes of Haze for Hawa

Two Class I Areas

Prepared by Dr. Marc Pitchford, NOA

for the USDA AAQTF meeting

11/15/05
Uses of IMPROVE Monitoring 

in the Regional Haze Rule

• IMPROVE Network has 110 particle spec

monitoring sites that nominally represent visibility-protected class I areas

• Each site collects every-third-day sample

PM2.5 for gravimetric and compositional a

and PM10 for gravimetric analysis

• Major particle components are used to es

current haze levels (used to establish basconditions and to track trends)

• All components are used to help identify t

sources (or source types & regions) that contribute to haze
Haleakula and Hawaii Volcano National Park Monit
Haze Indices 

• Light extinction (Mm-1) – loss of lig

unit distance due to scattering & absorption (directly related to aerosol 

concentration)

• Visual range (km) – largest distanc

a suitable object can be seen (invers

proportional to light extinction)

• Deciview haziness index (dv) – un

with respect to perceived haze chan

(logarithmic transformation of light extinc
Haze Levels from IMPROV

Network Particle Speciation D

• Light extinction associated with each of the majo

particle components is the component concentratimes an extinction efficiency (efficiency dependcomponent and the relative humidity)

• Total light extinction is the sum of the particle co

extinction values plus about 10Mm-1 for molecul

scattering of clean air

• The six major particle components – typical exti

efficiencies are: 

– Fine (PM2.5) ammonium sulfate – 3m

2/g (grows with hu

– Fine ammonium nitrate – 3m

2/g (grows with humidity)

– Fine organic compounds – 4m

2/g

– Fine elemental carbon – 10m

2/g

– Fine crustal compounds – 1m

2/g

– Coarse (PM(10-2.5)) mass – 0.6m

2/g
Growth curve used for ammonium sulfate and ammonium n

make them much for more efficient at high relative humidity. (growth for relative humidity greater than 95% is held consta
Hawaii IMPROVE Monitoring Site

Haleakula Hawaii Volcan
Haze & Ammonium Sulfate on Worst Haze Days for 2003 Hawaii Compar

Hawaii VolcHawaii VolcHaleakula – Haleakula – 
Hawaii Volcano IMPROVE Aerosol Extinction (2001 -2002

Worst Day Monthly Frequency Worst Day Monthly Averag

0

20406080

100120140160180

0

180

190185 195 200

205

210

215

220

225

230

235

240

245

250

255

260

265

270

275

280

285

290

295

300

305

310

315

320

325

330

335

340345 350355

FrequencySO2

Hawaii Volcano Mapfrom NPS Alert web site for 9:00am 4/7/05SO2 Pollution Rose & Wind Frequency 

for Visitor Center/IMPROVE Site for 2002
Hawaii Volcano Particulate vs Gaseous Sulfur

y = 0.014x + 0.187

R

2 = 0.6452

0123456

0 50 100 150 200 

SO2 Sulfur (ug/m3)

Ammonium Sulfate Sulfur (ug/m3)
Haleakula 

IMPROVE Monitoring Site on Maui

Site is about 3 miles NW of the Park boundary at an elevation of 3800’Park elevation range is 0’ to 10,023’
Haleakula IMPROVE Aerosol Extinction (2001 -2002)

Worst Day Monthly Frequency Worst Day Monthly Averaged C
Hawaii Volcano Plume is Still Intense Hundreds of Miles from its Source 
0

5

10152025

12/25/2001 4/4/2002 7/13/2002 10/21/2002 1/29/2003 5/9/2003 8/17/2003 

HAVO1HALE1

Sulfate Concentrations at the Two Hawaii IMPROVE Sites

Consistent trade winds

Consistent trade winds
Ammonium Sulfate for Hawaii IMPROVE Site

02468

1012141618

9/30/2003

10/3/2003

10/6/2003

10/9/2003

10/12/2003

10/15/2003

10/18/2003

10/21/2003

10/24/2003

10/27/2003

10/30/2003

11/2/2003

11/5/2003

11/8/2003

11/11/2003

11/14/2003

11/17/2003

11/20/2003

11/23/2003

Dates

Ammonium Sulfate (ug/m3)HAVO1 HALE1

Period with trajectory analysis
24-hour Forward Trajectories from the Volcano (starting mid-day H

Low sulfate at both sites for 10/15 sample period
Low at HALE 

but high at HAVO for 10/18 sample period.Low for both sites for Oct. 21 sample period
High for both 

sites for Oct. 24 sample period.
Highest at both 

sites for Oct. 27 sample period
High at both 

sites for Oct. 30 sample period.Typical trade winds produce trajectories like these for many of the following days when sulfate levels are low at both monitoring sites.

• This analys

demonstrates sulfate is likehaze on at leathe worst hazHaleakula.• How much Haleakula sulcaused by the 
Positive Matrix Factorizat

• PMF is a statistical method that identifies 

specified number of source profiles (i.e. rcomposition particle species for each souand source strengths for each sample pethat reduce the difference between measand PMF fitted PM2.5 mass concentration

• In matrix notation,

X = GF + E

where X is the matrix of measured compofor each sample period, F is the source pis the source strength or factor scores for sample period, and E is the residual or ermatrix.
PMF application to Hawa

IMPROVE Particle Speciation 

• All available PM2.5 speciation data fo

sites (>2 years each) are used togetthe PMF to explain measured PM2.5 

• Six factors seemed to separate reas

explained source factors

• Multiple linear regression was used 

explain coarse mass using the six Pfactors 
Six Source Profiles from Hawaii PMF An

0.000.100.200.300.400.50

A l A s B r Ca E C1 E C2 E C3 O C1 O C2 O C3 O C4 O P Cl Cr Cu H Fe P b M g M n Ni NO 3 P K Rb S e S i 

0.000.050.100.150.20

Al A s B r Ca E C1 EC2 E C3 OC1 OC2 OC3 OC4 OP Cl Cr Cu H Fe P b M g M n Ni NO3 P K Rb Se S i 

0.000.050.100.150.20

Al As Br Ca EC1 EC2 EC3 OC1 OC2 OC3 OC4 OP Cl Cr Cu H Fe Pb Mg Mn Ni NO3 P K Rb Se Si 

0.000.050.100.150.200.25

Al As Br Ca EC1 EC2 EC3 OC1 OC2 OC3 OC4 OP Cl Cr Cu H Fe Pb Mg Mn Ni NO3 P K Rb Se Si 

0.000.010.010.020.020.030.030.04

Al As Br Ca EC1 EC2 EC3 OC1 OC2 OC3 OC4 OP Cl Cr Cu H Fe Pb Mg Mn Ni NO3 P K Rb Se Si 

0.000.050.100.150.200.25

Al As Br Ca EC1 EC2 EC3 OC1 OC2 OC3 OC4 OP Cl Cr Cu H Fe Pb Mg Mn Ni NO3 P K Rb Se Si 

#1, Sea salt#3, Dust#4, Smoke#5, Secondary Nitrate#6, Secondary Sulfate & Nitrate#2, Volcano sulfate
Coarse Mass to PM2.5 Ratios 

(Based on Multiple Linear Regression of Coarse Mass on the Fa

0

0.5

1

1.5

2

2.5

12345

Source Factor

CM/PM2.5

Sea Salt

Volcano Sulfate

Dust

Smoke

Secondary NitrateSecondary Sulfate (Urban and/or Pow
05

1015202530354045

0 5 10 15 

Calculated PM2

Measured PM2.5

y = 0.9421x + 0.1034

R2 = 0.7407

02468

101214

0123456789

Calculated PM2.5

Measured PM2.5

Measured vs. Calculated PM2.5

Haleakula Hawaii Volcano

This shows that the 6 PMF factors provide a good fit to the PM2.5 mea
Contributions to PM2.5 by Source Factors

1

7%

2

33%

3

8%

4

22%

5

14%

6

16%

1

7%

2

70%

3

3%

4

7%

5

6% 67%

1

2%

2

41%

3

7%

4

19%

5

11%

6

20%

2

88%

5

4% 4

3%

3

1%

6

3%

1

1%

All Days Worst 20% Haze Days

Volcano

Sea salt

Dust Smoke

Nitrate

Sulfate & Nitrate
0

5

1015202530

1/3

1/9

1/21

1/27

1/30

3/7

3/10

3/13

3/16

3/25

4/3

4/6

9/21

9/24

10/3

10/18

10/24

10/27

10/30

11/23

11/29

12/17

12/20

12/26

2003 Date

PM2.5 (ug/m3)

Series6Series5Series4Series3Series2Series1

012345678

1/9

1/27

1/30

2/5

3/7

3/31

4/3

4/6

5/24

5/27

5/30

6/5

7/14

7/17

8/7

8/22

9/24

10/3

10/24

10/27

10/30

12/20

12/23

2 0 0 3 D a te

PM2.5 (ug/m3)

S eries 6S eries 5S eries 4S eries 3S eries 2S eries 1

Contributions of Source Factors to PM2.5 in 20% Worst Da

Haleakula

Hawaii Volcano

At Haleakuof worst haassociated emissions, others are with differe(e.g. smokesulfate and 

At Hawaii worst haze dominated volcano su

Note that Octob30 had trajectorvolcano to Hale
PMF Next Steps 

• Assess credibility of the non-volcano fact

Haleakula

– Is the smoke factor elevated during known bu

events?

– Is the dust factor primarily local emission acti

&/or high winds, or global dust impacts?

– What sources are associated with the nitrate 

the sulfate/nitrate (#6) factors?

• Incorporate coarse mass & convert factor

contribution to light extinction for both mosites

– Want to separate coarse mass from local ma

activities from Asian dust, sea salt, & other nasources

– Need to weigh emissions control priorities ba

haze contributions
Local verses Global OC/EC Im

(a proposed conceptual mo

• Because Hawaii is on islands in the midd

the Pacific Ocean

– All the fine OC and EC is either local or globa

is some small amount of oceanic OC) 

– Global OC/EC probably from large biogenic f

should affect both Hawaii sites to the same emost of the time

– Local OC/EC can affect one site but probably 

other site

• Differences between the two sites for fine 

and coarse mass should be an indicator oimpact

• When both sites measure relatively high 

global dust is a likely explanation
HALE-HAVO Elemental Carbon

-0.15-0.10-0.05

0.000.050.100.150.200.25

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Haleakula Elemental Carbon (ug/m3)

Delta Elemental Carbon (ug/m3)

HALE-HAVO Organic Carb

-2.00-1.50-1.00-0.50

0.000.501.001.502.002.50

0.00 0.50 1.00 

Haleakula Organic Carb

Delta Organic Carbon (ug/m3)

HALE-HAVO Elemental Carbon

-0.15-0.10-0.05

0.000.050.100.150.200.25

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20

Hawaii Volcano Elemental Carbon (ug/m3)

Delta Elemental Carbon (ug/m3)

HALE-HAVO Organic Carb

-2.00-1.50-1.00-0.50

0.000.501.001.502.002.50

0.00 0.50 1.00 

Hawaii Volcano Organic C

Delta Organic Carbon (ug/m3)
O rg a n ic C a rb o n

0.000.501.001.502.002.50

12/30/2001 2/28/2002 4/29/2002 6/28/2002 8/27/2002 10/26/20

D a te

Organic Carbon (ug/m3)

HH

E le m e n ta l C a rb o n

0.000.050.100.150.200.250.30

12/30/2001 2/28/2002 4/29/2002 6/28/2002 8/27/2002 10/26/20

D a te

Elemental Carbon (ug/m3)

HaHa
Haleakula Elemental Carbon vs Organic Carbon Mass

y = 0.1108x + 0.0251

R2 = 0.5559

0.000.050.100.150.200.250.300.35

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

Organic Carbon Mass (ug/m3) 

Elemental Carbon (ug/m3)

Hawaii Volcano Elemental Carbon vs Organic Carbon Mass

y = 0.0612x - 0.0026

R2 = 0.2925

0.000.050.100.150.200.250.30

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

Organic Carbon Mass (ug/m3) 

Elemental Carbon (ug/m3)

• The ratio of elecarbon to organic Haleakula is largHawaii Volcano.• Also the correlstronger at HaleaHawaii Volcano.• Haleakula is exhave smoke and combustion sourthat would providorganic and elem• Its seems that Volcano must hasource contributicarbon with little elemental carbon secondary organ
Summary

• The volcanic emissions of sulfate domina

haze measured at Hawaii Volcano Nation

• It is also the single largest source of wors

conditions at Haleakula National Park

• There are other sources of haze that are 

significantly contributing on worst haze daHaleakula

– PMF analysis indicates that smoke, dust and 

volcanic sulfur and nitrate sources are import

– These need to be better understood and tied 

specific sources or source activities to be use

• More assessment work is needed and 

suggestions are welcome.
Causes of Haze Assessme

--Nation-Wide--

• Data analysis similar to that done fo

Hawaii’s two visibility-protected arearegional scale air quality modeling is conducted by Regional Planning Organizations for all such areas to sdevelopment of Regional Haze State Implementation Plans due in 2007