Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada

Stable isotope techniques may be a suitable tool for tracing industrial emissions in the atmosphere and the environment provided that the isotopic compositions of industrial emissions are distinct. We determined the isotopic compositions of nitrate, ammonium and sulfate in PM2.5 emitted from two ind...

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Main Authors: Proemse, Bernadette, Mayer, B., Chow, J., Watson, J.
Format: Journal Article
Published: Pergamon 2012
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S1352231012006097
http://hdl.handle.net/20.500.11937/32751
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author Proemse, Bernadette
Mayer, B.
Chow, J.
Watson, J.
author_facet Proemse, Bernadette
Mayer, B.
Chow, J.
Watson, J.
author_sort Proemse, Bernadette
building Curtin Institutional Repository
collection Online Access
description Stable isotope techniques may be a suitable tool for tracing industrial emissions in the atmosphere and the environment provided that the isotopic compositions of industrial emissions are distinct. We determined the isotopic compositions of nitrate, ammonium and sulfate in PM2.5 emitted from two industrial stacks at a large upgrader site in the Athabasca oil sands region (AOSR), northeastern Alberta, Canada, and compared them to the nitrogen and sulfur isotopic compositions of source materials and upgrading by-products. We found distinct isotopic compositions of nitrate and ammonium in PM2.5 compared to those reported for atmospheric nitrate and ammonium in the literature. Nitrate in PM2.5 had d15N values of 9.4& (Stack A) and 16.1 1.2& (Stack B) that were significantly enriched in 15N compared to the feedstock materials (w2.5&), by-products of upgrading (0.3e1.3&), and atmospheric N2 (0&). d15N of ammonium in PM2.5 showed a large range with values between 4.5 to þ20.1& (StackB). We report the first measurements of the triple oxygen isotopic composition of industrial emitted nitrate. Nitrate emitted as PM2.5 is not mass-independently enriched in 17O resulting inD17O ¼ 0.5 0.9& (Stack B) and is therefore distinct from atmospheric nitrate, constituting an excellent indicator of industrial derived nitrate. d18O values of nitrate in PM2.5 (36.0 and 17.6 1.8& for Stack A and B, respectively) were also significantly lower than d18O values of atmospheric nitrates and hence isotopically distinct. d34S values of sulfate in PM2.5 were with 7.3 0.3& (Stack A) and 9.4 2.0& (Stack B) slightly enriched in 34S compared to d34S in bitumen (4.3 0.3&) and coke (3.9 0.2&). d18O values of sulfate in PM2.5 were 18.9 2.9& and 14.2 2.8& for Stack A and Stack B, respectively. The isotopic composition of sulfate in PM2.5 was not sufficiently different from d34S and d18O values of sulfate in longrange atmospheric deposition in industrial countries to serve as a quantitative indicator for industrial emitted PM2.5.We conclude that d18O and D17O values of nitrate in stack-emitted PM2.5 are excellent, and d15N values of nitrate and ammonium are suitable indicators for identifying and tracing of PM2.5 nitrate and ammonium emitted from two stacks in the AOSR in the surrounding terrestrial and aquatic ecosystems.
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spelling curtin-20.500.11937-327512017-02-28T01:49:35Z Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada Proemse, Bernadette Mayer, B. Chow, J. Watson, J. Ammonium Nitrate Athabasca oil sands Alberta Industrial emissions Sulfate Stable isotope techniques may be a suitable tool for tracing industrial emissions in the atmosphere and the environment provided that the isotopic compositions of industrial emissions are distinct. We determined the isotopic compositions of nitrate, ammonium and sulfate in PM2.5 emitted from two industrial stacks at a large upgrader site in the Athabasca oil sands region (AOSR), northeastern Alberta, Canada, and compared them to the nitrogen and sulfur isotopic compositions of source materials and upgrading by-products. We found distinct isotopic compositions of nitrate and ammonium in PM2.5 compared to those reported for atmospheric nitrate and ammonium in the literature. Nitrate in PM2.5 had d15N values of 9.4& (Stack A) and 16.1 1.2& (Stack B) that were significantly enriched in 15N compared to the feedstock materials (w2.5&), by-products of upgrading (0.3e1.3&), and atmospheric N2 (0&). d15N of ammonium in PM2.5 showed a large range with values between 4.5 to þ20.1& (StackB). We report the first measurements of the triple oxygen isotopic composition of industrial emitted nitrate. Nitrate emitted as PM2.5 is not mass-independently enriched in 17O resulting inD17O ¼ 0.5 0.9& (Stack B) and is therefore distinct from atmospheric nitrate, constituting an excellent indicator of industrial derived nitrate. d18O values of nitrate in PM2.5 (36.0 and 17.6 1.8& for Stack A and B, respectively) were also significantly lower than d18O values of atmospheric nitrates and hence isotopically distinct. d34S values of sulfate in PM2.5 were with 7.3 0.3& (Stack A) and 9.4 2.0& (Stack B) slightly enriched in 34S compared to d34S in bitumen (4.3 0.3&) and coke (3.9 0.2&). d18O values of sulfate in PM2.5 were 18.9 2.9& and 14.2 2.8& for Stack A and Stack B, respectively. The isotopic composition of sulfate in PM2.5 was not sufficiently different from d34S and d18O values of sulfate in longrange atmospheric deposition in industrial countries to serve as a quantitative indicator for industrial emitted PM2.5.We conclude that d18O and D17O values of nitrate in stack-emitted PM2.5 are excellent, and d15N values of nitrate and ammonium are suitable indicators for identifying and tracing of PM2.5 nitrate and ammonium emitted from two stacks in the AOSR in the surrounding terrestrial and aquatic ecosystems. 2012 Journal Article http://hdl.handle.net/20.500.11937/32751 http://www.sciencedirect.com/science/article/pii/S1352231012006097 Pergamon restricted
spellingShingle Ammonium
Nitrate
Athabasca oil sands
Alberta
Industrial emissions
Sulfate
Proemse, Bernadette
Mayer, B.
Chow, J.
Watson, J.
Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title_full Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title_fullStr Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title_full_unstemmed Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title_short Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada
title_sort isotopic characterization of nitrate, ammonium and sulfate in stack pm2.5 emissions in the athabasca oil sands region, alberta, canada
topic Ammonium
Nitrate
Athabasca oil sands
Alberta
Industrial emissions
Sulfate
url http://www.sciencedirect.com/science/article/pii/S1352231012006097
http://hdl.handle.net/20.500.11937/32751