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

SLIDE 1

ASITA-2014

Anna Smirnoff1, Martine M. Savard1, Robert Vet2, and Marie-Christine Simard1

1Geological Survey of Canada, 490 rue de la Couronne, Quebec (Quebec), G1K 9A9 2Environment Canada 4905 Dufferin Street Toronto (Ontario), M3H 5T4

1942

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A Triple-Ratios Characterization of Nitrogen- Containing Compounds in Atmospheric samples from Alberta Using Chemical Conversion and Thermal Decomposition of N2O

SLIDE 2

Objectives

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

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SLIDE 3

NOx Souces in Northern Alberta

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Atmospheric sources of nitrogen-bearing compounds

Characterized by δ15N, δ17O and δ18O

Transport Agriculture

Gas compressors and gas plants

Coal-Fired Power Plants Upgraders OS Operations

Desulphurization and hydrogen plants, boilers, heaters, turbines, vehicles, etc.

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4

Sample Types

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Sample type Sampler Directional

NO3

Wet-only

No NH4

+

Wet-only No Gaseous NH3 Filterpack (citrated cellulose) Yes Particle NO3

Filterpack (Teflon)

Yes Particle HN4

+

Filterpack (Teflon) Yes Gaseous NO2 and NOx Maxxam (Resins) No Gaseous HNO3 Filterpack (Nylon) Yes

SLIDE 5

Analytical Approach

Characterize nitrogen compounds using triple
xygen 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 (NO2-)
Convert NO2
into N2O
Decompose N2O into N2 and O2
Obtain results for δ15N, δ17O, δ18O
Normalize results using International standards

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Sampling Area 1: (Southwest of Edmonton)

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Sundance Keephills Genesee

Alberta coal-fired power plants emissions

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Sampling Area 2: (Vauxhall, SW Alberta)

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Gas compressor stations (NOx and NO2

)

SLIDE 8

Sampling Area 3: (Edmonton)

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Keephills Sundance Airport Sewage Treatment Plant

359o

Terrace Heights,

City of Edmonton sampling Sector

City/Traffic emissions

210o

Genesee

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Sampling Area 4: (Fort Saskatchewan)

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Emissions from Upgraders facilities

354° 267° 20°

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Sample Preparation

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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

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Sample Preparation using Chemical Approach

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Conversion of NO3
to NO2
(passing sample through Cd-

reduction column)

Reduce NO2
to N2O using NaN3

(sodium azide)

Analyze N2O using our modified

Pre-Con with a gold furnace

18.5 cm 25 cm 10 cm 5-cm ID 85 mL 2-mm ID 3.5-mm ID Cu-Cd granules Glass wool plug

SLIDE 12 1942

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Analytical Setup

vent

He

vent

Mg(ClO4 )2 + NaOH water trap Mg(ClO4 )2

He

LH2

manual

Valco 6 port

vent

U

LH2

auto

He

RT-Q Bond Plot, 15m

LH2

auto Modified from Brand,1995

MoleSieve GC Column, 30m

To IRMS

U U Pre-Con Gold Furnace

SLIDE 13

Results from the system

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Dual Isotope Results Particulates and Gases

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30 40 50 60 70 80 90

8.0
6.0
4.0
2.0

0.0 2.0 4.0 6.0 8.0 10.0 12.0

δ18O δ15N δ15N vs δ18O in NO3 (particulates)

Genesee, CFPP Vauxhall, Gas copr.

Terr. Heights, URBAN

Fort Sask. Fort Sask.

30 40 50 60 70 80 90

10
8
6
4
2

2 4 6 8 10

δ18O δ15N δ15N vs δ18O in NO3 (HNO3-gas)

Genesee, CFPP Vauxhall, Gas copr.

Terr. Heights, URBAN

Fort Sask.

SLIDE 15 1942

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Triple Isotope Results for (Gaseous and Particulates)

HNO3

gases

Genesee, CFPP

NO3

(particulates)

Vauxall, Gas Comp. Terrace Heights, Urban Fort Saskat., Upgraders Genesee, CFPP

NO3

in particulates

Genesee, CFPP Vauxall, Gas Comp Terrace Heights, Urban Fort Saskat., Upgraders

HNO3

(gas)

SLIDE 16

Conclusions

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

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SLIDE 17

C’est tout!

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The End