ASITA-2014 L I G O O G L I O C A G L S N U O R I - PowerPoint PPT Presentation

N A A D C A 1942 G E U E O Q ASITA-2014 L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O A Triple-Ratios Characterization of Nitrogen- Containing Compounds in Atmospheric samples from Alberta Using Chemical Conversion and Thermal Decomposition of N 2 O Anna Smirnoff 1 , Martine M. Savard 1 , Robert Vet 2 , and Marie-Christine Simard 1 1 Geological Survey of Canada, 490 rue de la Couronne, Quebec (Quebec), G1K 9A9 2 Environment Canada 4905 Dufferin Street Toronto (Ontario), M3H 5T4

N A A D C A 1942 G E U E O Q Objectives L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O Project “SOURCES” ( SOurce apportionment Using isotope Ratio Characterization of oil sands Environmental Samples) :  Better understand the terrestrial N cycle and the fate of atmospheric N-species Presentation  Characterize the 4 main sources of O-bearing airborne N contaminants in 4 Albertan settings

N A A D C A 1942 NO x Souces in Northern G E U E O Q L I G O O G L I O C Alberta A É G L S N U O R I V S E S Y I M - M C O Atmospheric sources of nitrogen-bearing compounds  Characterized by δ 15 N, δ 17 O and δ 18 O Desulphurization and hydrogen plants, boilers, heaters, turbines, vehicles, etc. OS Operations Gas Coal-Fired Agriculture Transport Upgraders compressors Power Plants and gas plants

N A A D C A 1942 G E U E O Q L I G Sample Types O O G L I O C A É G L S N U O R I V S E S Y I M - M C O Sample type Sampler Directional - NO 3 Wet-only No + NH 4 Wet-only No Gaseous NH 3 Filterpack (citrated cellulose) Yes Particle NO 3 - Filterpack (Teflon) Yes Particle HN 4 + Filterpack (Teflon) Yes Gaseous NO 2 and NO x Maxxam (Resins) No Gaseous HNO 3 Filterpack (Nylon) Yes 4

N A A D C A 1942 G E U E O Q Analytical Approach L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O  Characterize nitrogen compounds using triple oxygen and nitrogen isotopic ratios:  Collect various nitrogen compounds in wet, dry and gaseous forms at different locations  Convert all samples into solution for further treatment  Convert all N-species into one form (NO 2 - )  Convert NO 2 - into N 2 O  Decompose N 2 O into N 2 and O 2  Obtain results for δ 15 N, δ 17 O, δ 18 O  Normalize results using International standards

N A A D C A 1942 Sampling Area 1: G E U E O Q L I G O O G L I O C A É (Southwest of Edmonton) G L S N U O R I V S E S Y I M - M C O Sundance Keephills Genesee Alberta coal-fired power plants emissions 6

N A A D C A Sampling Area 2: 1942 G E U E O Q L I G O O G L I O C A É (Vauxhall, SW Alberta) G L S N U O R I V S E S Y I M - M C O - ) Gas compressor stations (NO x and NO 2 7

N A A D C A 1942 Sampling Area 3: G E U E O Q L I G O O G L I O C A É (Edmonton) G L S N U O R I V S E S Y I M - M C O 359 o Terrace Heights, City of Edmonton sampling Sector Sundance Sewage Treatment Plant Keephills Airport Genesee 210 o City/Traffic emissions

N A A D C A 1942 Sampling Area 4: G E U E O Q L I G O O G L I O C A É (Fort Saskatchewan) G L S N U O R I V S E S Y I M - M C O 20° 354° 267° 9 Emissions from Upgraders facilities

N A A D C A 1942 G E U E O Q L I G Sample Preparation O O G L I O C A É G L S N U O R I V S E S Y I M - M C O  Very few labs can analyze triple oxygen and nitrogen…  Methods of sample preparation and analysis are described in article published in 2012 in “Rapid Communications in Mass Spectrometry”  The procedure can be divided into a few major steps 10

N A A D C A Sample Preparation using 1942 G E U E O Q L I G O O G L I O C A É Chemical Approach G L S N U O R I V S E S Y I M - M C O 10 cm 5-cm ID 85 mL  Conversion of NO 3 - to NO 2 - (passing sample through Cd- reduction column) 2-mm ID  Reduce NO 2 - to N 2 O using NaN 3 25 cm (sodium azide) 18.5 cm 3.5-mm ID  Analyze N 2 O using our modified Pre-Con with a gold furnace Cu-Cd granules Glass wool plug 11

N A A D C A 1942 G E U E O Q Analytical Setup L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O vent vent vent To IRMS He water trap Mg(ClO 4 ) 2 MoleSieve GC Column, 30m Valco 6 port He Mg(ClO 4 ) 2 + NaOH RT-Q Bond Plot, 15m He auto auto manual U U U Gold LH 2 LH 2 LH 2 Furnace Pre-Con Modified from Brand,1995

N A A D C A 1942 G E U E O Q L I Results from the system G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O

N A A D C A Dual Isotope Results 1942 G E U E O Q L I G O O G L I O C A É Particulates and Gases G L S N U O R I V S E S Y I M - M C O δ 15 N vs δ 18 O in NO 3 (HNO 3 -gas) 90 Vauxhall, Gas copr. Genesee, CFPP 80 Fort Sask. δ 18 O 70 60 50 Terr. Heights, URBAN 40 30 -10 -8 -6 -4 -2 0 2 4 6 8 10 δ 15 N δ 15 N vs δ 18 O in NO 3 (particulates ) 90 80 Vauxhall, Gas copr. Genesee, CFPP δ 18 O 70 Fort Sask. 60 50 Terr. Heights, URBAN 40 Fort Sask. 30 -8.0 -6.0 -4.0 -2.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 δ 15 N

N A A D C A Triple Isotope Results for 1942 G E U E O Q L I G O O G L I O C A É G (Gaseous and Particulates) L S N U O R I V S E S Y I M - M C O - in particulates - gases NO 3 HNO 3 - (particulates) NO 3 (gas) HNO 3 Genesee, CFPP Genesee, CFPP Genesee, CFPP Vauxall, Gas Comp. Vauxall, Gas Comp Terrace Heights, Fort Saskat., Urban Upgraders Terrace Heights, Urban Fort Saskat., Upgraders

N A A D C A 1942 G E U E O Q Conclusions L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O  Triple isotope characterization offers a great potential for distinguishing N-sources:  coal-fired plants  urban transportation  upgraders  Potential for understanding modification processes and fate of N contaminants

N A A D C A 1942 G E U E O Q The End L I G O O G L I O C A É G L S N U O R I V S E S Y I M - M C O C’est tout!