Glacier National Park Garden Wall viewed from southern Lake McDonald s shore

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1 Spatial and Seasonal Patterns in Speciated Fine Particle Concentration in the Rural United States Bret Schichtel NPS Glacier National Park Garden Wall viewed from southern Lake McDonald s shore Aerosol conc. = 12 µg/m 3 William Malm NPS Marc Pitchford NOAA/EPA Lowell Ashbaugh UCD Robert Eldred UCD Rodger Ames CIRA Aerosol conc. = 21.7 µg/m 3 Aerosol conc. = 65.3 µg/m 3 IMPROVE Monitoring Program The Interagency Monitoring of Protected Visual Environments A cooperative measurement effort of particulate matter and haze in Class I Areas Governed by representatives from Federal and regionalstate organizations Objectives: Establish current visibility and aerosol conditions in federal class I areas Identify chemical species and emission sources responsible for existing man-made visibility impairment in FCIA Document long-term trends for assessing progress towards the national visibility goal to FCIA With the enactment of the Regional Haze Rule, to provided regional haze monitoring representing all visibility-protected FCIA Conduct visibility/aerosol research: Intensive monitoring studies Began operating in spring of 1988 with 2 monitoring sites Today has 165 sites - 54 sites with seven or more years of data. 1

2 Chiricahua, NM IMPROVE Aerosol Monitor carbonate denuder Module A Module B Module C Module D PM2.5 PM2.5 PM 2.5 PM1 (Teflon) (Nylon) (Quartz) (Teflon) mass, elements absorption sulfate, nitrate ions organic, elemental carbon mass electrical to controller electrical to controller electrical to controller electrical to controller Other Instruments: Optical measurements using transmissometers and nephelometers Color photography to document the scene Aerosol Composite Components Reconstructed Fine Mass Ammonium Sulfate * [S] Ammonium Nitrate 1.29 * [NO 3 ] Organics 1.4 [OC] Elemental Carbon [EC] Soil 2.2[Al]+2.49[Si]+1.63[Ca]+2.42[Fe]+1.94[Ti] Soil potassium =.6[Fe], FeO and Fe2O3 are equally abundant. A factor of 1.16 is used for other component Reconstructed Fine Mass (mg/m3) RCFM = Sulfate + Nitrate + Organics + EC + Soil Addison Pinnacle, NY, y =.76x R 2 = Measured Fine Mass (mg/m3) Reconstructed Fine Mass (mg/m3) Connecticut Hill, NY, y =.82x R 2 = Measured Fine Mass (mg/m3) µg/m 3 2

3 Annual Ammonium Sulfate - 21 Annual Organic (1.4*OC) - 21 IMPROVE Elemental Carbon - 21 Winter 21, Dec, Jan, Feb OC/EC Ratio Summer 21, Jun, Jul, Aug OC/EC ratio varies between 3-5, indicative of more primary urban emissions OC/EC > 7 throughout upper West and Texas, Fires? OC/EC ~ 3 in Industrial Midwest, primary urban? OC/EC > 4-6 in southeast, increased secondary organics? 3

4 Biogenic vs Fossil Carbon Summer of 22 at Yosemite National Park Biogenic or fossil carbon content in aerosol ( µg/m 3 ) y = x R=.9969 Biogenic carbon mass Fossil carbon mass Election Microscopic images of Carbon Particles Yosemite NP, August Total carbon content in aerosol ( µg/m 3 ) C12 - Old Carbon C14 - New Carbon C14 half life ~ 5 years Chain of soot particles stuck to an agglomerate of organic tar balls Organic particles with sulfate inclusions (Transmission Election Microscope Annual Ammonium Nitrate - 21 Yosemite NP Ionic Concentrations PILS 15 minute ion data from the PILS inlet Yosemite PILS (7/14/3-9/5/3) neq/m NH4+ NO3- SO4= Na /14 7/16 7/18 7/2 7/22 7/24 7/26 7/28 7/3 8/1 8/3 8/5 8/7 8/9 8/11 8/13 8/15 8/17 8/19 8/21 8/23 8/25 8/27 8/29 8/31 9/2 9/4 9/6 Date 4

5 Big Bend NP Size Distributions - August 1999 Annual Fine Soil Nitrate found in coarse mode particles Mode size ~4-5 µm Size distribution similar to Na + PM 2.5 includes tail of coarse mode 2- SO 4 dc/dlogdp (neq/m 3) SO4= Cl NO D(µm) 15 2 Cl - -, NO 3 dc/dlogdp (neq/m 3) NH4+ NH 4 + dc/dlogdp (neq/m 3) 1 5 Na+ K+ Mg2+ Ca Na +, K +, M g 2+, Ca 2+ dc/dlogdp (neq/m 3) D aero (µm) Monthly Average Species Concentrations Began operating in spring of 1988 with 2 monitoring sites Today has 165 sites - 54 sites with seven or more years of data. 5

6 Monthly Average Species Concentrations Monthly Average Species Concentrations Data and Information Distribution Visualization and Analysis Websites END 6

7 Percent Change in 8th Percentile Sulfate Concentrations Percent Change in 2th Percentile Sulfate Concentrations NET SO 2 Emission Trends SO 2 and SO 4 Comparison 7

8 Concentration, ug/m NH4+_ug/m3 NO3-_ug/m3 SO4=_ug/m3 5 Bondville 4 2/3 NO 3- and SO 2-4 both important NH 4 NO 3 in submicron mode Average Concentration, neq/m < Aerodynamic Diameter, µm NO3-, neq/m3 SO4=, neq/m3 Na+, neq/m3 NH4+, neq/m >18. San Gorgonio /3 Large diurnal variability 5 Submicron NH 4 NO 3 dominant Concentration, neq/m3 Average Concentration, neq/m NO3-, neq/m3 SO4=, neq/m3 Na+, neq/m3 NH4+, neq/m3 < >18. Aerodynamic Diameter, µm 7 NH 4+, neq/m3 6 NO3-, neq/m3 SO4=, neq/m /2/23 2/3/23 2/4/23 2/5/23 2/6/23 2/7/23 2/8/23 2/9/23 2/1/23 2/11/23 2/12/23 2/13/23 Date 2/14/23 2/15/23 2/16/23 2/17/23 2/18/23 2/19/23 2/2/23 2/21/23 2/22/23 2/23/23 4/4 4/5 4/6 4/7 4/8 4/9 4/1 4/11 4/12 4/13 4/14 4/15 4/16 4/17 4/18 4/19 4/2 4/21 4/22 4/23 4/24 4/25 4/26 4/27 San Gorgonio 7/3 Grand 12 Canyon 1 Grand Canyon More regular diurnal variability Some days sulfate-dominated 3 NO3-, ug/m3 SO4=, ug/m3 NH4+, ug/m3 K+, ug/m3 K+ spikes Nitrate in coarse mode Appears to be associated with Na + and Ca 2+ Concentration (neq/m3) Na+ (neq/m3) Grand Canyon MOUDI average Cl- NO3- + Clsea salt Concentration, ug/m3 2 1 neq/m SO4= NH4+ NO3- Na+ Ca2+ 2 7/2 7/3 7/4 7/5 7/6 7/7 7/8 7/9 7/1 7/11 7/12 7/13 7/14 7/15 7/16 7/17 7/18 7/19 7/2 7/21 7/22 7/23 7/24 7/25 7/26 7/27 7/28 7/29 < >18. aerodynamic diameter (µm) 8

9 IMPROVE Aerosol Samplers Four independent sampling modules Prior to 2, two 24 hour samples were collected twice a week, after 2, samples collected every three days. Module A B C D Filter Teflon Nylon Quartz Teflon Size PM2.5 PM2.5 PM2.5 PM1 Variable mass Na-Mn Fe-Pb total H optical absorption sulfate, nitrate OC, EC in 8 fractions mass Analysis gravimetric Proton Induced X-Ray Emission X-ray Fluorescence Proton Elastic Scattering Hybrid Integrating Plate/Sphere Ion Chromatography Thermal Optical Reflectance gravimetric Source Profiles for OC/EC Gillies, Gertler, Sagebiel, and Dippel (21) EST 35, 154: Tunnel measurements yield OC/EC = 2.66 McDonald, Zielinska, Fujita, Sagebiel, Chow, and Watson (2) EST 34 28: Colorado hardwoods yield OC/EC =11 Washington DC Raw OC EC Data Jarbidge Raw OC EC Data 9

10 Great Smoky Raw OC EC Data Thermal Optical Reflectance IMPROVE collects fine particulates on a quartz filter which is analyzed for organic and elemental carbon in 7 temp. bands. Elemental carbon is operationally defined as carbon evolved after oxygen is added to the environment and reflectance returns to initial value (pyrolysis correction), i.e. light absorbing carbon. TEMPERATURE (deg C) Initial Reflectance Organic Carbon Elemental Carbon 2% O Temperature 98% is He 2 held -25 Second constant Delay within each band until all carbon has Pyrolized Carbon evolved. Maximum This time Charring varies Carbon on filter Evolved loading. 1% He Begin Charring Methane Reference Peak Laser Reflectance Temperature FID Output OCLT OCHT ECLT ECHT O3 E1 O2 O4 O1 P E2 E TIME (sec) 24 IMPROVE and EPA Speciated Trend Network (STN) IMPROVE 165 monitoring sites in mostly rural areas STN - 25 m- 3 monitoring sites in mostly urban/suburban areas IMPROVE Corrects OC and EC for a Positive Artifact IMPROVE: Artifact Corrected OC ~.3, EC ~.2 µg/m 3 Carbon Mass (µg/m 3 ) Shenandoah, VA 1999, IMPROVE Light Abs. Carbon 4 Organic Carbon Fine Particle Mass (µg/m 3 ) EPA STN monitoring site: No carbon artifact correction Burlington, VT 21, EPA STN 8 SASS_EC 7 SASS_OC 6 The positive artifact correction causes the organic and elemental carbon to approach zero as fine mass goes to zero Carbon Mass (µg/m 3 ) Fine Particle Mass (µg/m 3 ) 1

11 IMPROVE and STN Fine Mass Budgets Reconstructed fine mass: = [Amm. Sulfate] + [Amm.Nitrate] + [Soil] + 1.4[Organic Carbon] + [Light Abs Carbon] OC is scaled by 1.4 to account for oxygen Washington, and hydrogen DC 21 mass - IMPROVE 1% OC accounts for ~2% of fine mass at Washington, ~43% at Baltimore 8% EC accounts for ~6% of fine mass at Washington, ~4.4% at Baltimore 6% Percent Fine mass 4% 2% % Jan Mar May Jul Sep Nov Organic EC Amm. Sulfate Amm. Nitrate Soil Other Percent Fine mass 12% 1% 8% 6% 4% 2% Baltimore, MD 21 - STN % Jan Mar May Jul Sep Nov Organic EC Amm. Sulfate Amm. Nitrate Soil Other IMPROVE modules A, B, C IMPROVE module D inlet stack annular denuder (Module B only, to remove nitric acid) hose from solenoid manifold to critical orifice and pump inlet tee stack compression sleeve timing pulleys for motor hand wheel to raise solenoid manifold motor drive to raise solenoid manifold solenoid valve (4) solenoid manifold cartridge with 4 filter cassettes cassette manifold cyclone stack to PM1 inlet electronics enclosure cartridge with 4 cassettes motor drive to lower solenoid manifold stack compression sleeve retainer pin cassette manifold solenoid manifold hose from solenoid manifold to critical orifice and pump solenoid valve (4) critical orifice critical orifice connector for hose to pump electronics enclosure connector for line to controller hand wheel to lower solenoid manifold timing pulleys for motor electrical connector (front) and hose connector (rear) 11

12 IMPROVE Monitoring Monitoring Began in March 1988 Optical extinction by transmissometer &/or scattering by nephelometer (hourly) plus absorption on particle filters (24-hour) Aerosol particle sampling/analysis for six major species & trace constituents to aid in source attribution (24 hour samples twice weekly; every 3 rd day starting in 2) Scene color photography to document scenic appearance (typically 3 photos/day) photographic spectrums of a range of visibility conditions are generated from 5 years of photos Organic Carbon Elemental Carbon IMPROVE Seasonal EC and OC Winter 21, Dec, Jan, Feb Summer 21, Jun, Jul, Aug Conclusions Spatial Patterns The largest carbon concentrations are in the southeastern US, but the largest carbon fine mass fractions are in the northwestern US The urban carbon excess appears to have a limited spatial extent OC/EC ratios imply: Winter carbon aerosol is not biogenic (fire or secondary organics) Summer carbon aerosol High OC/EC ratio in the Northwest - smoke Low OC/EC ratio in Ohio River Valley - urban/industrial Middling OC/EC ration in Southeastern US - mix of urban, fire, biogenic. The Regional Haze Rule Federal class I areas (including national parks, other wilderness areas) to return to natural visibility conditions by 264 Implementation 2% worst haze days are to be brought back to natural conditions 2% best haze days are to remain unchanged Baseline haze calculated from 2-24 period State Implementation Plans to be submitted by 27 for linear improvement in visibility over the period 12

13 Regional Haze Rule: Coarse Mass Budget Husar, 22 Natural haze: natural windblown dust, biomass smoke and other natural processes Man-made: industrial activities AND man-perturbed smoke and dust emissions Trick: to identify what is natural and what sources are responsible for man made fraction Sulfate mass fraction=.89 Nitrate mass fraction=.69 OC mass fraction=.289 LAC mass fraction=.15 Soil mass fraction=.538 Missing mass fraction=