# Kentucky Energy and Environment Cabinet

Kentucky Division for Air Quality



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Appendix B.6

Continuous Measures of

Speciated PM2.51July 23, 2007Patricia Brewer1, Scott Reynolds2,Roger Tanner3, Eric Edgerton4, Ben Hartsell4,Jim Renfro5, Hoke Kimball6, John Calcagni71VISTAS2South Carolina Department of Health and Environmental Control3Tennessee Valley Authority4Atmospheric Research Associates5National Park Service6North Carolina Department of Natural Resources7Environmental Protection AgencyVISTAS Special Monitoring StudiesContinuous Measures of Speciated PM2.52Presentation Objectives• Special Monitoring Studies• Continuous Monitors: PM2.5, Sulfate,Nitrate, Total Carbon, Black Carbon3Monitoring ObjectivesUse continuous monitors of PM2.5mass,sulfate, nitrate, total carbon and blackcarbon to characterize daily and spatialtrendsData collected Mar 2003 - Dec 2004Raw data available in AQSNormalized data available from VISTASDraft VISTAS Report authored by RogerTanner, TVAURBANCLASS 1Great Smoky Mtns.Cape RomainRaleighVISTAS Focus SitesAtlanta5March 2003 - December 2004• Continuous monitoring:• Sulfate, Nitrate, Total Carbon (R&P instruments)• Black Carbon (Aethalometer)• Continuous Mass (TEOM)• Precursor gases - SO2, NOy, CO• Light Scattering (Nephelometer) at Class 1areas)• Meteorology• Alternative Sulfate and Nitrate methods• Filter-based Speciation:IMPROVE or STNFocus Sites6Lessons Learned fromContinuous Monitors• Continuous PM2.5 mass (TEOM) showsgood agreement to PM2.5 mass from filter7PM2.52003y = 1.3336x + 3.3987R2= 0.8542y = 1.0749x + 2.8358R2= 0.9629y = 0.8383x + 2.4046R2= 0.9051010203040500 10 20 30 40 50Filter

ContinuousMassContinuous PM2.5 mass shows good agreement to PM2.5 mass from filter8Lessons Learned fromContinuous Monitors• Aethalometer (BC) has good performance• R&P instruments for S, N, and Total C achievedgood data capture (>75%) when operating• Periodic failures R&P instruments• S, N, TC, BC continuous data needs to benormalized to filter-based data to interpret trends.• Correlations by Site and Quarter• Continuous speciated monitors have highupkeepand data management• Postscript: R&P monitors are being discontinued• Alternative commercial continuous monitors9V IS T A S F o c u s S ite T E O M P M2 5Q 3 200301 02 03 04 05 06 07 /17 /8 7 /1 5 7 /2 2 7 /2 98 /5 8 /1 2 8 /1 9 8 /2 69 /29 /99 /1 6 9 /2 3 9 /3 0

micrograms / cubic meterDK PMMB PMCR PMLR PMThird Quarter 2003V IS T A S F o c u s S ite S u lfa te200301 02 07/1 7/8 7/15 7/22 7/29 8/5 8/12 8/19 8/26 9/2 9/9 9/16 9/23 9/30

micrograms / cubic meterMB SO 4CR SO4LR SO 4MASSSULFATE10V IS T A S F o c u s S ite T o ta l C a rb o n200301 07/1 7/8 7/15 7/22 7/29 8/5 8/12 8/19 8/26 9/2 9/9 9/16 9/23 9/30

micrograms / cubic meterMB TCCR TCLR TCThird Quarter 2003V IS T A S F o c u s S ite T E O M P M2 5Q 3 200301 02 03 04 05 06 07 /17 /8 7 /1 5 7 /2 2 7 /2 98 /5 8 /1 2 8 /1 9 8 /2 69 /29 /99 /1 6 9 /2 3 9 /3 0

micrograms / cubic meterDK PMMB PMCR PMLR PMMASSCARBON11Lessons Learned fromContinuous Monitors• Continuous monitors high scattercompared to filter-based data• Capture same spatial and seasonaltrends as filter-based data12Filter comparisonsSulfate - IMPROVELook Rock SulfateQ3 200305101520257/1 7/8 7/15 7/22 7/29 8/5 8/12 8/19 8/26 9/2 9/9 9/16 9/23 9/30

micrograms / cubic mete rLR SO4fLR SO413Filter comparisonsSulfate - IMPROVECape Romain SulfateQ3 200305101520257/1 7/8 7/15 7/22 7/29 8/5 8/12 8/19 8/26 9/2 9/9 9/16 9/23 9/30

micrograms / cubic mete rCR SORfCR SO414Filter comparisonsSulfate – STNRVEMillbrook SulfateQ3 200305101520257/1 7/8 7/15 7/22 7/29 8/5 8/12 8/19 8/26 9/2 9/9 9/16 9/23 9/30

micrograms / cubic mete rMB STN SO4MB SO415Sulfate2003y = 1.0079x + 0.7062R2= 0.6451y = 0.6538x + 1.2038R2= 0.7711y = 0.5623x + 0.6845R2= 0.77750510152005101520Filter

ContinuousSulfate16Nitrate2003y = 0.322x + 0.1088R2= 0.1171y = 0.9853x + 0.0657R2= 0.7019y = 0.5556x + 0.1306R2= 0.35290.00.51.00.0 0.5 1.0Filter

ContinuousNitrate17Carbon2003y = 0.783x + 0.7507R2= 0.6823y = 1.2608x + 0.4168R2= 0.5383y = 0.4249x + 1.0943R2= 0.759904812160 4 812 16Filter

ContinuousTotalCarbon18Elemental Carbon2003y = 0.6704x + 0.7892R2= 0.6108y = 1.0152x + 0.5788R2= 0.4042y = 0.2646x + 0.8859R2= 0.59104812160 4 812 16Filter

ContinuousElementalto BlackCarbon19Normalizing ContinuousMonitoring Data• Continuous data was normalized to filterdata to facilitate comparison to modeledvalues• Regressions calculated for each site, eachquarter20Lessons Learned fromContinuous Monitors• Diurnal and seasonal trends:• Sulfate:• GRSM > MILL > ROMA in summer• Little regional difference other seasons• Consistent with regionally distributed sources• Highest in summer at all sites• Afternoon peak in warm seasons, not otherseasons• Consistent with photochemical production21Diurnal Pattern of Average Sulfate in Winter (Jan-Mar) 2004at Focus Sites0.01.02.03.04.05.000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[SO 4

= ], μ g/m

3ROMAGRSMMILL22Diurnal Pattern of Average Sulfate in Spring (Apr-Jun) 2004at Focus Sites0.01.02.03.04.05.06.07.08.000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[SO 4

= ], μ g/m

3ROMAGRSMMILL23Diurnal Pattern of Average Sulfate in Summer (Jul – Sep) 2004at Focus Sites0.01.02.03.04.05.06.07.08.09.000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[SO 4

= ], μ g/m

3ROMAGRSMMILL24Diurnal Pattern of Average Sulfate in Fall (Oct – Dec) 2004at Focus Sites0.01.02.03.04.05.000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[SO 4

= ], μ g/m

3ROMAGRSMMILL25Lessons Learned fromContinuous Monitors• Diurnal and seasonal trends:• Nitrate:• Highest in winter, lowest in summer• Seldom greater than 1μg/m3except winter• Consistent with temperature dependency• MILL > ROMA > GRSM• Dawn peak at MILL, before rush hour• Consistent with high RH before dawn• Local sources26Diurnal Pattern of AverageNitrate in Winter 2004at Focus Sites0.000.501.001.502.002.503.0000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[NO3-], ug/m3ROMA 2004GRSM 2004MILL 200427Diurnal Pattern of Average Nitrate in Spring atFocus Sites0.000.200.400.600.801.001.201.401.6000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[NO 3

- ], μ g/m

3ROMA 2003GRSM 2003MILL 2003ROMA 2004GRSM 2004MILL 200428Diurnal Pattern of Average Nitrate in Summer atFocus Sites0.000.100.200.300.400.500.600.700.800.901.0000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[NO 3

- ], μ g/m

3ROMA 2003GRSM 2003MILL 2003ROMA 2004GRSM 2004MILL 200429Diurnal Pattern of Average Nitrate in Fallat Focus Sites0.000.200.400.600.801.001.201.401.6000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[NO 3

- ], μ g/m

3ROMA 2003GRSM 2003MILL 2003ROMA 2004GRSM 2004MILL 200430Lessons Learned fromContinuous Monitors• Diurnal and seasonal trends:• Black Carbon• Similar loadings in all seasons• Dekalb > MILL > GRSM = ROMA• Peaks correspond to AM and PM rush hours inurban areas• Primary emissions, local sources,• Total Carbon• MILL > GRSM = ROMA• At GRSM, TC and OC are slightly higher in summerthan other seasons; other sites show no seasonaltrend31Diurnal Pattern of Average Black Carbon in Springat Focus Sites0.000.501.001.502.002.503.003.5000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[BC], μ g/m

3ROMA 2003GRSM 2003MILL 2003Dekalb 2003ROMA 2004GRSM 2004MILL 2004Dekalb 200432Diurnal Pattern in AverageBlack Carbon in Summerat Focus Sites0.00.51.01.52.02.53.000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[BC], μ g/m

3ROMA 2003GRSM 2003MILL 2003Dekalb 2003ROMA 2004GRSM 2004MILL 2004Dekalb 200433Diurnal Pattern in Average Black Carbon in Fallat Focus Sites0.000.501.001.502.002.503.0000:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00Hour of Day

[BC], ug/m3ROMA 2003GRSM 2003MILL 2003Dekalb 2003ROMA 2004GRSM 2004MILL 2004Dekalb 200434Next StepsFinalize draft report for VISTASContinuous MonitoringAdditional analyses?Compare diurnal trends from continuousdata (2003, 2004) to CMAQ model diurnaltrends (2002)Use monthly averages since different yearsCompare trends to SEARCH dataSubmit manuscript for publication