Measuring Total Reactive N and its Composition Bret A. Schichtel 1, Katie Benedict 2, Christian M. Carrico 2, Anthony Prenni 2, Jr. 2, Ezra Levin 2, Derek Day 3, Doris Chen 2, John Ray 1, William C. Malm 3, Krisiti Gebhart 1, Mike Barna 1, Jeffrey L. Collett 2, Sonia M. Kreidenweis 2 1 National Park Service, CSU/CIRA, Fort Collins, Colorado 80523 2 Department of Atmospheric Science, Colorado State University 3 Cooperative Institute for Research in the Atmosphere (CIRA), CSU
Long-Term Reactive Nitrogen Deposition Assessment Goals Important (deposition levels and bioavailability) reactive nitrogen constituents deposited in sensitive ecosystem are known Methods to measure important constituents suitable for routine monitoring networks are developed Models to simulate total reactive nitrogen deposition in sensitive ecosystem and its composition are developed Tools to assess the causes for excess reactive nitrogen deposition, e.g. source apportionment, are developed
Measuring Total Chemically Reactive N TCRN = NOy + NHx (Oxidized) (Reduced) NOy NO + NO 2 + NO 3 + 2xN 2 O 5 + HNO 3 + HONO + HO 2 NO 2 + R-ONO 2 (organic nitrates such as PAN and alkyl nitrates) + R-ONO (organic nitrites) + NO 3 - (particulate nitrate). NHx = NH 3 + NH 4 + amines (R-NHx) + HCN (acetonitrile) + other reduced organic molecules Everything but N 2 O and N 2
NPS and Collaborators Efforts to Develop Methods and Understand Missing Components ROMANS II Characterization of total RN deposition and its sources at Rocky Mtn NP; Nov 2008-Nov 2009 GrandTReNDS - Characterization of total RN deposition and its sources in Grand Teton NP; April Sep 2011 Begin to address some needs listed in the table: Quantify the contribution of organic N to total N deposition Speciated organic and inorganic wet and dry N flux in areas relevant to critical loads research IMPROVE NH4, NH3, & amines measurement study, Apr 11 Aug 12 CSU- CO Front Range passive NH3 network Modeling reactive N in Rocky Mountains using CAMx; Barna et al., Snow pack chemistry George Ingersoll will send 2011-12 snow pack samples to CSU to be analyzed for ON, NO3, NH4, SO4and analyzed for chemistry New fine particulate total nitrogen measurement (Chow and Watson, DRI)
GrandTReNDS (April Sept 2011) Grand Tetons Reactive Nitrogen Deposition Study Grand Teton NP Personnel Forest Service Personnel Grand Targhee Ski Area Planning NPS: Bret Schichtel, Ellen Porter, Mike Barna, Kristi Gebhart, William Malm CSU: Jeff Collet, Sonia Kreidenweis Data Collection and Analysis Derek Day Yi Li Amy Sullivan Tony Prenni Doris Chen Ezra Levin, Yury Desyaterik, Misha Schurman, Taehyoung Lee
To identify issues, develop solutions, and track changes in N deposition: Determine the total nitrogen deposition in Grand Teton and its composition Any past or future projections based on incomplete data assumes the omitted fraction is small, remains constant in time, or highly correlated with measured N Determine the origin of deposited nitrogen N Deposition in Yellowstone (Teton) has increased Why? Increased natural emissions from fires or climate change? Increased anthropogenic emission? What important anthropogenic sources are likely to change? Bill in Idaho House to strengthen Right to Farm Act: The bill would make it easier for farmers to enlarge their feedlot operations but more difficult for opponents to challenge those plans in court (Intermountain Farm & Ranch, 966 March 4 th, 2011)
GrandTReNDS Grand Tetons Reactive Nitrogen Deposition Study Grand Targhee Snowfall ~50 feet by mid-april
Targhee Ski Resort Daily URG Daily HiVol Precipitation Met Station Passive, PILS Gas Rack Sizing Rack, AMS 4/21 (lower) 7/27-9/20 (upper) Driggs Daily URG Precipitation Passive (NH 3 & HNO 3 ) Met. Station 4/6 9/20/2011 Passive (NH 3 & HNO 3 ) (2 week and 4 week) 7/21 9/20/2011 Precipitation Passive (NH 3 & HNO 3 ) 7/5 9/20/2011 Passive (NH 3 & HNO 3 ) 7/5 9/20/2011 Daily URG Daily HiVol Precipitation Met Station Passive (NH 3 & HNO 3 ) 5/15 9/20/2011
Passive Ammonia Concentrations, µg/m 3 1.4 Idaho/Wyoming Border FR 8.9 8.2 8.6 3.2 Driggs 3.3 Driggs SB GT HL SL DC NC MJ TS 9.8 6.5 Craters of the Moon RP 4.8 Bell, Allen, et al., Craters of the Moon Passive NH3 Study; June 17, 2010 to July 1, 2010 GrandTReNDS Passive NH3 Study, July 7 (27) - Sep 20, 2011
Deposition Pathways site comparison DR: July 27 - Sept. 21 Wet NO3 20% NH4 2% Wet NH4 27% NO3 0% Wet ON 11% HNO 3 4% NH3 36% GT: July 27 Driggs: - Sept. April 21 6- Sept. NC: 21 July 27- Sept. 21 NH4 2% Wet NO3 17% Wet NH4 29% NO3 0% Wet ON NH3 0.36 28% Wet 13% ON 16% Wet NO3- HNO 0.41 14% 3 8% HNO3 0.09 3% NH4+ 0.05 2% NH3 0.92 33% NO3-0.01 NH4 0% 2% Wet NO3 18% Wet NH4 29% NO3 0% Wet NH4+ 0.97 35% Wet ON 18% HNO 3 6% NH3 27%
Total Water Soluble Particulate Organic nitrogen WSON = TN (NO 2 - + NO 3 - + NH 4+ ) Total water soluble N Shimadzu TOC V CSH total organic carbon analyzer with a total nitrogen module NO 2-, NO 3-, NH 4 + ion chromatography Individual organic nitrogen compounds Liquid Chromatography with Time of Flight Mass Spectrometry using electrospray ionization PM2.5 Hivol samplers Benedict et al., 2011
Total Water Soluble Particulate Organic Nitrogen Grand Targhee
Total Water Soluble Particulate Organic Nitrogen Rocky Mountain NP Benedict et al., 2011
IMPROVE NHx and Methylamine Monitoring Sites April 2011-Aug 2012 Using IMPROVE infrastructure: Site operators, RTI performing IC analysis CSU (Collett et al.,) is coordinating monitoring, QA/QC, data reduction, filter prep
Monthly Average NHx (1-in-3 day sampling), Apr Dec 2011 Doris Chen, et al.,
Monthly Average Methylamine (1-in-3 day sampling) Doris Chen, et al.,
Yellowstone, WY Daily (3 rd day) NH3 concentrations Rocky Mtn, CO Cedar Bluff, KS Bondville, IL Chiricahua, AZ
Chiricahua National Monument NH X * Chiricahua Annual 2006 NH3 emissions
Horseshoe 2 Fire Start: May 8th Containment: June 25th, 2011 June 8 th June 14 th
Total Particulate Nitrogen Judy Chow and John Watson Desert Research Institute (DRI), Reno NV DRI conducts all IMPROVE and CSN filter analysis to measure fine particulate carbonaceous aerosols Thermal Optical Reflectance (TOR) carbon analyzer measures OC and EC on quartz fiber filters Instrument can be modified to measure total particulate carbon, sulfur, hydrogen, oxygen and nitrogen
Grabowsky et al., 2011) Thermal Optical Reflectance (TOR) Particulate Carbon Analyzer
Potential configuration for next generation of thermal/optical analysis for elemental and optical properties Flow Control Network He, CH4 UV-VIS-NIR Light Source (λ=200-2000 nm) Filter Thermocouple Oven Filter Loading Push Rod He, O2, NO, SO2 He Optical Fibers 98% He,2% O2 Optical Spectrometer (Reflectance) Flow Splitter Filter Holder Optical Spectrometer (Transmittance) O Reactor (C/Ni) O CO Unoxidized species H 2 O/Gas Trap Soda Lime Mg(ClO 4) 2 CHNS Reactor (MnO 2 ) C CO 2, H H 2 O, N NO x /N 2, S SO 2 Oxidation Oven (CuO) CO CO2 Oxidation Oven (CuO) CO CO2 Heated Fused Silica Capillary NDIR CO 2 Detector Mass Spectrometer Vent Four-Way Solenoid Valve Outputs: Reflectance/ Transmittance Spectra O Mass Spectra C, H, N, S Calibration Gases Carrier/Reaction Gases
C,H,N,S, and O can be determined using current processes Carbon Mass by Elemental Analyzer (µg) Ion Signal (a.u.) NDIR Signal (mv) 1.2e+6 1.0e+6 8.0e+5 1.2e+5 1.0e+5 8.0e+4 6.0e+4 4.0e+4 2.0e+4 0.0 500 400 100 80 60 40 (b) (a) 140 C 100% He 98% He / 2% O 2 840 C m/z=44 (CO + 2 ) 740 C 280 C Temperature 480 C 580 C Calibration CH 4 Injection m/z=28 (CO +, N 2 + ) m/z=18 (H 2 O + ) m/z=30 (NO + ) m/z=64 (SO 2 + ) 20 40 60 80 Time (min) time vs Temp Time vs m/z18 NDIR Time vs m/z28 Time vs m/z30 Time vs m/z64 480 C 280 C 140 C Temperature 100% He 580 C Calibration O 2 Injection 20 40 60 80 Time (min) 1000 800 600 400 200 0 1000 800 600 400 200 0 Oven Temperature ( C) Oven Temperature ( C) Thermogram of Fresno ambient aerosol sample for (a) CHNS, and (b) O following the IMPROVE_A protocol. Comparison of carbon fractions measured by elemental analyzer and DRI thermal/optical carbon analyzer 6 5 4 3 2 1 0 EC3 y = 0.926x - 0.104 R² = 0.989 OC1 EC2 OC4 OC2 OC3 1:1 Line 0 1 2 3 4 5 6 Carbon Mass by Carbon Analyzer (µg) EC1
Expected N (µg) Expected S (µg) Expected C (µg) 90 80 70 60 50 40 30 20 10 C,H,N,S Calibration of MS-TOA using Sulfanilamide (C 6 H 8 N 2 O 2 S) C: y = 22.81x R² = 0.99 0 0.0 1.0 2.0 3.0 4.0 Normalized m/z=44 (CO 2+ ) Signal Expected H (µg) 10 8 6 4 2 H: y = 99.94x R² = 0.98 0 0.00 0.02 0.04 0.06 0.08 0.10 Normalized m/z=18 (H 2 O + ) Signal 32 28 24 20 16 12 N: y = 98.84x R² = 0.99 40 35 30 25 20 15 S: y = 59.07x R² = 0.96 8 10 4 5 0 0.0 0.1 0.2 0.3 0.4 Normalized m/z=30 (NO + ) Signal 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 Normalized m/z=64 (SO 2+ ) Signal
Total Fine Particulate Organic Nitrogen IMPROVE measures particulate nitrate and could measure ammonium Particulate ON (PON) = Total N f(n_no3) f(n_nh4) Water insoluble PON = PON water soluble PON DRI has unsuccessfully submitted proposals for additional instrument development
Questions? Grand Targhee Resort, top of Sacagawea lift
Species of interest Measured Routinely : HNO 3, particle NO 3 and NH 4 Wet: NO 3-, NH 4 + *NH 3 Missing Species *NO x (NO and NO 2 ) *Can be (starting to be) measured in routine network ~Components can be measured in special studies ~Reduced organic gases (Aliphatic amines..) ~Oxidized organic gases (PAN - alkyl nitrates ) ~Reduced and oxidized organic nitrogen containing particulates Wet Species *Total organic nitrogen Oxidized and reduced organic compounds ~Occult deposition
Why the Missing Components Matter Deposition (Spring) ON (estimated) 10% NOx NH3 4% Total Deposition Budget (Spring) 9% 1% 3%? Wet Wet ON 20% Measured NO3 4% NH4 12% NH3 37% NH3 NOx ON Gas/particles NO3 NH4 HNO3 7% Wet NH4 Wet NO3 20% ON Gas/particles (estimated) 34% Missing 26% NOx 13% ROMANS data