Causes of Haze for Hawaii’sTwo Class I AreasPrepared by Dr. Marc Pitchford, NOAAfor the USDA AAQTF meeting11/15/05Uses of IMPROVE Monitoring Datain the Regional Haze Rule• IMPROVE Network has 110 particle speciationmonitoring sites that nominally represent 155visibility-protected class I areas• Each site collects every-third-day samples ofPM2.5for gravimetric and compositional analysisand PM10for gravimetric analysis• Major particle components are used to estimatecurrent haze levels (used to establish baselineconditions and to track trends)• All components are used to help identify thesources (or source types & regions) thatcontribute to hazeHaleakulaandHawaii VolcanoNational Park Monitoring SitesHaze Indices•Light extinction (Mm-1)– loss of light perunit distance due to scattering &absorption(directly related to aerosolconcentration)•Visual range (km)– largest distance thata suitable object can be seen(inverselyproportional to light extinction)•Deciview haziness index (dv)– uniformwith respect to perceived haze changes(logarithmic transformation of light extinction)Haze Levels from IMPROVENetwork Particle Speciation Data• Light extinction associated with each of the majorparticle components is the component concentrationtimes an extinction efficiency (efficiency depends on thecomponent and the relative humidity)• Total light extinction is the sum of the particle componentextinction values plus about 10Mm-1for molecularscattering of clean air• The six major particle components – typical extinctionefficiencies are:– Fine (PM2.5) ammonium sulfate – 3m2/g (grows with humidity)– Fine ammonium nitrate – 3m2/g (grows with humidity)– Fine organic compounds – 4m2/g– Fine elemental carbon – 10m2/g– Fine crustal compounds – 1m2/g– Coarse (PM(10-2.5)) mass – 0.6m2/gGrowth curve used for ammonium sulfate and ammonium nitratemake them much for more efficient at high relative humidity.(growth for relative humidity greater than 95% is held constant)Hawaii IMPROVE Monitoring SiteHaleakula Hawaii VolcanoHaze & Ammonium Sulfate on Worst Haze Days for 2003 Hawaii Compared to Lower 48Hawaii Volcano – 77Mm-1Hawaii Volcano – 8.1μg/m3Haleakula – 36Mm-1Haleakula – 3.4μg/m3Hawaii Volcano IMPROVE Aerosol Extinction (2001 -2002)Worst Day Monthly Averaged CompositionWorst Day Monthly Frequency02040608010012014016018005101520253035404550556065707580859095100105110115120125130135140145150155160165170175180185190195200205210215220225230235240245250255260265270275280285290295300305310315320325330335340345350355FrequencySO2Hawaii Volcano Mapfrom NPS Alert web site for 9:00am 4/7/05SO2Pollution Rose & Wind Frequencyfor Visitor Center/IMPROVE Site for 2002Hawaii Volcano Particulate vs Gaseous Sulfury = 0.014x + 0.187R2= 0.645201234560 50 100 150 200 250SO2 Sulfur (ug/m3)

Ammonium Sulfate Sulfur (ug/m3 )HaleakulaIMPROVEMonitoringSite on MauiSite is about 3miles NW of thePark boundaryat an elevationof 3800’Park elevationrange is 0’ to10,023’Haleakula IMPROVE Aerosol Extinction (2001 -2002)Worst Day Monthly FrequencyWorst Day Monthly Averaged CompositionHawaii Volcano Plume is Still Intense Hundredsof Miles from its Source – Satellite Image051015202512/25/2001 4/4/2002 7/13/2002 10/21/2002 1/29/2003 5/9/2003 8/17/2003 11/25/2003HAVO1HALE1Sulfate Concentrations at the Two Hawaii IMPROVE SitesConsistenttrade windsConsistenttrade windsInterestingperiodAmmonium Sulfate for Hawaii IMPROVE Sites024681012141618 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 11/26/2003 11/29/2003 12/2/2003 12/5/2003Dates

Ammonium Sulfate (ug/m3)HAVO1HALE1Period with trajectory analysis24-hour Forward Trajectories from the Volcano (starting mid-day Hawaii time)Low sulfate atboth sites for10/15 sampleperiodLow at HALEbut high atHAVO for10/18 sampleperiod.Low for bothsites for Oct.21 sampleperiodHigh for bothsites for Oct.24 sampleperiod.Highest at bothsites for Oct. 27sample periodHigh at bothsites for Oct.30 sampleperiod.Typical tradewinds producetrajectories likethese for manyof the followingdays whensulfate levelsare low at bothmonitoringsites.•This analysisdemonstrates that volcanicsulfate is likely impactinghaze on at least some ofthe worst haze days forHaleakula.•How much of theHaleakula sulfate iscaused by the volcano?Positive Matrix Factorization• PMF is a statistical method that identifies a userspecified number of source profiles (i.e. relativecomposition particle species for each source)and source strengths for each sample periodthat reduce the difference between measuredand PMF fitted PM2.5mass concentration• In matrix notation,X = GF + Ewhere X is the matrix of measured compositionfor each sample period, F is the source profile, Gis the source strength or factor scores for eachsample period, and E is the residual or errormatrix.PMF application to HawaiiIMPROVE Particle Speciation Data• All available PM2.5speciation data for bothsites (>2 years each) are used together inthe PMF to explain measured PM2.5mass• Six factors seemed to separate reasonablyexplained source factors• Multiple linear regression was used toexplain coarse mass using the six PMFfactorsSix Source Profiles from Hawaii PMF Analysis0.000.100.200.300.400.50A 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 Na S r S Ti V Zn0.000.050.100.150.20Al 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 Na S r S Ti V Zn0.000.050.100.150.20Al 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 Na Sr S Ti V Zn0.000.050.100.150.200.25Al 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 Na Sr S Ti V Zn0.000.010.010.020.020.030.030.04Al 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 Na Sr S Ti V Zn0.000.050.100.150.200.25Al 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 Na Sr S Ti V Zn#1, Sea salt#3, Dust#4, Smoke#5, Secondary Nitrate#6, Secondary Sulfate & Nitrate#2, Volcano sulfateCoarse Mass to PM2.5Ratios(Based on Multiple Linear Regression ofCoarse Mass on the Factor Scores)00.511.522.5123456Source Factor

CM/PM2.5Sea SaltVolcano SulfateDustSmokeSecondaryNitrateSecondary Sulfate and Nitrate(Urban and/or Power Plant)y = 1.0152x - 0.0551R2= 0.81930510152025303540450 5 10 15 20 25 30Calculated PM2.5

Measured PM2.5y = 0.9421x + 0.1034R2= 0.7407024681012140123456789Calculated PM2.5

Measured PM2.5Measured vs. Calculated PM2.5HaleakulaHawaii VolcanoThis shows that the 6 PMF factors provide a good fit to the PM2.5measurements.Contributions to PM2.5by Source Factors17%233%38%422%514%616%17%270%33%47%56%67%12%241%37%419%511%620%Haleakula288%54%43%31%63%11%HawaiiVolcanoAll Days Worst 20% Haze DaysVolcanoSea saltDustSmokeNitrateSulfate & NitrateSite051015202530 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/ 2 4 10 / 3 10/ 1 8 10 / 24 10/27 10/ 3 0 11/ 23 11/29 12/ 1 7 12/ 20

1 2/ 262003 Date

PM2.5 (ug/m3)Series6Series5Series4Series3Series2Series1012345678 1/9 1/2 7 1/3 0 2/5 3 / 7 3/3 1 4/ 3 4/6 5/2 4

5 /2 7 5/3 0 6 / 5 7/1 4 7 / 17 8 / 7 8/22 9 / 24 10 /3 10/24 10/27 10/30 12/20 1 2 / 2 32 0 0 3 D a te

PM2.5 (ug/m3)S eries 6S eries 5S eries 4S eries 3S eries 2S eries 1Contributions of Source Factors toPM2.5 in 20% Worst Days of 2003HaleakulaHawaii VolcanoAt Haleakula, about halfof worst haze days areassociated with volcanoemissions, while theothers are associatedwith different factors(e.g. smoke, secondarysulfate and nitrate)At Hawaii Volcano, allworst haze days aredominated by thevolcano sulfate factor.Note that October 24, 27, &30 had trajectories from thevolcano to HaleakulaPMF Next Steps• Assess credibility of the non-volcano factors forHaleakula– Is the smoke factor elevated during known burningevents?– Is the dust factor primarily local emission activities&/or high winds, or global dust impacts?– What sources are associated with the nitrate (#5) andthe sulfate/nitrate (#6) factors?• Incorporate coarse mass & convert factors tocontribution to light extinction for both monitoringsites– Want to separate coarse mass from local man-madeactivities from Asian dust, sea salt, & other naturalsources– Need to weigh emissions control priorities based onhaze contributionsLocal verses Global OC/EC Impacts(a proposed conceptual model)• Because Hawaii is on islands in the middle ofthe Pacific Ocean– All the fine OC and EC is either local or global (thereis some small amount of oceanic OC)– Global OC/EC probably from large biogenic firesshould affect both Hawaii sites to the same extent,most of the time– Local OC/EC can affect one site but probably not theother site• Differences between the two sites for fine soiland coarse mass should be an indicator of localimpact• When both sites measure relatively high levelsglobal dust is a likely explanationHALE-HAVO Elemental Carbon-0.15-0.10-0.050.000.050.100.150.200.250.00 0.05 0.10 0.15 0.20 0.25 0.30Haleakula Elemental Carbon (ug/m3)

Delta Elemental Carbon (ug/m3)HALE-HAVO Organic Carbon Mass-2.00-1.50-1.00-0.500.000.501.001.502.002.500.00 0.50 1.00 1.50 2.00 2.50Haleakula Organic Carbon (ug/m3)

Delta Organic Carbon (ug/m3)HALE-HAVO Elemental Carbon-0.15-0.10-0.050.000.050.100.150.200.250.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20Hawaii Volcano Elemental Carbon (ug/m3)

Delta Elemental Carbon (ug/m3)HALE-HAVO Organic Carbon Mass-2.00-1.50-1.00-0.500.000.501.001.502.002.500.00 0.50 1.00 1.50 2.00 2.50Hawaii Volcano Organic Carbon (ug/m3)

Delta Organic Carbon (ug/m3)O rg a n ic C a rb o n0.000.501.001.502.002.5012/30/2001 2/28/2002 4/29/2002 6/28/2002 8/27/2002 10/26/2002 12/25/2002D a te

Organic Carbon (ug/m3)Hawaii VolcanoHaleakulaE le m e n ta l C a rb o n0.000.050.100.150.200.250.3012/30/2001 2/28/2002 4/29/2002 6/28/2002 8/27/2002 10/26/2002 12/25/2002D a te

Elemental Carbon (ug/m3)Hawaii VolcanoHaleakulaHaleakula Elemental Carbon vs Organic Carbon Massy = 0.1108x + 0.0251R2= 0.55590.000.050.100.150.200.250.300.350.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00Organic Carbon Mass (ug/m3)

Elemental Carbon (ug/m3)Hawaii Volcano Elemental Carbon vs Organic Carbon Massy = 0.0612x - 0.0026R2= 0.29250.000.050.100.150.200.250.300.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00Organic Carbon Mass (ug/m3)

Elemental Carbon (ug/m3)• The ratio of elementalcarbon to organic carbon atHaleakula is larger than atHawaii Volcano.• Also the correlation is muchstronger at Haleakula than atHawaii Volcano.• Haleakula is expected tohave smoke and othercombustion source impactsthat would provide bothorganic and elemental carbon.• Its seems that HawaiiVolcano must have some localsource contributing organiccarbon with little or noelemental carbon (e.g.secondary organics)Summary• The volcanic emissions of sulfate dominates thehaze measured at Hawaii Volcano National Park• It is also the single largest source of worst hazeconditions at Haleakula National Park• There are other sources of haze that aresignificantly contributing on worst haze days atHaleakula– PMF analysis indicates that smoke, dust and nonvolcanic sulfur and nitrate sources are important– These need to be better understood and tied tospecific sources or source activities to be useful• More assessment work is needed andsuggestions are welcome.Causes of Haze Assessment--Nation-Wide--• Data analysis similar to that done forHawaii’s two visibility-protected areas andregional scale air quality modeling is beingconducted by Regional PlanningOrganizations for all such areas to supportdevelopment of Regional Haze StateImplementation Plans due in 2007