Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument
The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen-containing particles impact atmospheric chemistry, air quality, and ecological N deposition. Instruments that measure total reactive nitrogen (N<sub>r</sub&...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2018-05-01
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| Series: | Atmospheric Measurement Techniques |
| Online Access: | https://www.atmos-meas-tech.net/11/2749/2018/amt-11-2749-2018.pdf |
| _version_ | 1818084108505448448 |
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| author | C. E. Stockwell C. E. Stockwell A. Kupc A. Kupc B. Witkowski B. Witkowski B. Witkowski R. K. Talukdar R. K. Talukdar Y. Liu V. Selimovic K. J. Zarzana K. J. Zarzana K. Sekimoto K. Sekimoto C. Warneke C. Warneke R. A. Washenfelder R. J. Yokelson A. M. Middlebrook J. M. Roberts |
| author_facet | C. E. Stockwell C. E. Stockwell A. Kupc A. Kupc B. Witkowski B. Witkowski B. Witkowski R. K. Talukdar R. K. Talukdar Y. Liu V. Selimovic K. J. Zarzana K. J. Zarzana K. Sekimoto K. Sekimoto C. Warneke C. Warneke R. A. Washenfelder R. J. Yokelson A. M. Middlebrook J. M. Roberts |
| author_sort | C. E. Stockwell |
| collection | DOAJ |
| description | The chemical composition of aerosol particles is a key aspect in determining their impact
on the environment. For example, nitrogen-containing particles impact
atmospheric chemistry, air quality, and ecological N deposition. Instruments
that measure total reactive nitrogen (N<sub>r</sub> = all nitrogen compounds
except for N<sub>2</sub> and N<sub>2</sub>O) focus on gas-phase nitrogen and
very few studies directly discuss the instrument capacity to measure the mass
of N<sub>r</sub>-containing particles. Here, we investigate the mass
quantification of particle-bound nitrogen using a custom N<sub>r</sub> system
that involves total conversion to nitric oxide (NO) across platinum and
molybdenum catalysts followed by NO−O<sub>3</sub> chemiluminescence detection.
We evaluate the particle conversion of the N<sub>r</sub> instrument by
comparing to mass-derived concentrations of size-selected and counted
ammonium sulfate ((NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>), ammonium nitrate
(NH<sub>4</sub>NO<sub>3</sub>), ammonium chloride (NH<sub>4</sub>Cl), sodium nitrate
(NaNO<sub>3</sub>), and ammonium oxalate ((NH<sub>4</sub>)<sub>2</sub>C<sub>2</sub>O<sub>4</sub>)
particles determined using instruments that measure particle number and size.
These measurements demonstrate N<sub>r</sub>-particle conversion across the
N<sub>r</sub> catalysts that is independent of particle size with
98 ± 10 % efficiency for 100–600 nm particle diameters. We also
show efficient conversion of particle-phase organic carbon species to
CO<sub>2</sub> across the instrument's platinum catalyst followed by a
nondispersive infrared (NDIR) CO<sub>2</sub> detector. However, the
application of this method to the atmosphere presents a challenge due to the
small signal above background at high ambient levels of common gas-phase
carbon compounds (e.g., CO<sub>2</sub>). We show the N<sub>r</sub> system is an
accurate particle mass measurement method and demonstrate its ability to
calibrate particle mass measurement instrumentation using single-component,
laboratory-generated, N<sub>r</sub>-containing particles below
2.5 µm in size. In addition we show agreement with mass
measurements of an independently calibrated online particle-into-liquid
sampler directly coupled to the electrospray ionization source of a
quadrupole mass spectrometer (PILS–ESI/MS) sampling in the negative-ion mode.
We obtain excellent correlations (<i>R</i><sup>2</sup> = 0.99) of particle mass
measured as N<sub>r</sub> with PILS–ESI/MS measurements converted to the
corresponding particle anion mass (e.g., nitrate, sulfate, and chloride). The
N<sub>r</sub> and PILS–ESI/MS are shown to agree to within ∼ 6 %
for particle mass loadings of up to 120 µg m<sup>−3</sup>. Consideration
of all the sources of error in the PILS–ESI/MS technique yields an overall
uncertainty of ±20 % for these single-component particle streams.
These results demonstrate the N<sub>r</sub> system is a reliable direct
particle mass measurement technique that differs from other particle
instrument calibration techniques that rely on knowledge of particle size,
shape, density, and refractive index. |
| first_indexed | 2024-12-10T19:48:39Z |
| format | Article |
| id | doaj.art-c5f48f0763ee448796fce7733521809d |
| institution | Directory Open Access Journal |
| issn | 1867-1381 1867-8548 |
| language | English |
| last_indexed | 2024-12-10T19:48:39Z |
| publishDate | 2018-05-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Measurement Techniques |
| spelling | doaj.art-c5f48f0763ee448796fce7733521809d2022-12-22T01:35:50ZengCopernicus PublicationsAtmospheric Measurement Techniques1867-13811867-85482018-05-01112749276810.5194/amt-11-2749-2018Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrumentC. E. Stockwell0C. E. Stockwell1A. Kupc2A. Kupc3B. Witkowski4B. Witkowski5B. Witkowski6R. K. Talukdar7R. K. Talukdar8Y. Liu9V. Selimovic10K. J. Zarzana11K. J. Zarzana12K. Sekimoto13K. Sekimoto14C. Warneke15C. Warneke16R. A. Washenfelder17R. J. Yokelson18A. M. Middlebrook19J. M. Roberts20NOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USAFaculty of Chemistry, University of Warsaw, al. Żwirki i Wigury 101, 02-089, Warsaw, PolandNOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry, University of Colorado Denver, Denver, CO 80217, USADepartment of Chemistry, University of Montana, Missoula, MT 59812, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USADepartment of Chemistry, University of Montana, Missoula, MT 59812, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USANOAA Earth System Research Laboratory (ESRL), Chemical Sciences Division, Boulder, CO 80305, USAThe chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen-containing particles impact atmospheric chemistry, air quality, and ecological N deposition. Instruments that measure total reactive nitrogen (N<sub>r</sub> = all nitrogen compounds except for N<sub>2</sub> and N<sub>2</sub>O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of N<sub>r</sub>-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom N<sub>r</sub> system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO−O<sub>3</sub> chemiluminescence detection. We evaluate the particle conversion of the N<sub>r</sub> instrument by comparing to mass-derived concentrations of size-selected and counted ammonium sulfate ((NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>), ammonium nitrate (NH<sub>4</sub>NO<sub>3</sub>), ammonium chloride (NH<sub>4</sub>Cl), sodium nitrate (NaNO<sub>3</sub>), and ammonium oxalate ((NH<sub>4</sub>)<sub>2</sub>C<sub>2</sub>O<sub>4</sub>) particles determined using instruments that measure particle number and size. These measurements demonstrate N<sub>r</sub>-particle conversion across the N<sub>r</sub> catalysts that is independent of particle size with 98 ± 10 % efficiency for 100–600 nm particle diameters. We also show efficient conversion of particle-phase organic carbon species to CO<sub>2</sub> across the instrument's platinum catalyst followed by a nondispersive infrared (NDIR) CO<sub>2</sub> detector. However, the application of this method to the atmosphere presents a challenge due to the small signal above background at high ambient levels of common gas-phase carbon compounds (e.g., CO<sub>2</sub>). We show the N<sub>r</sub> system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single-component, laboratory-generated, N<sub>r</sub>-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated online particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS–ESI/MS) sampling in the negative-ion mode. We obtain excellent correlations (<i>R</i><sup>2</sup> = 0.99) of particle mass measured as N<sub>r</sub> with PILS–ESI/MS measurements converted to the corresponding particle anion mass (e.g., nitrate, sulfate, and chloride). The N<sub>r</sub> and PILS–ESI/MS are shown to agree to within ∼ 6 % for particle mass loadings of up to 120 µg m<sup>−3</sup>. Consideration of all the sources of error in the PILS–ESI/MS technique yields an overall uncertainty of ±20 % for these single-component particle streams. These results demonstrate the N<sub>r</sub> system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index.https://www.atmos-meas-tech.net/11/2749/2018/amt-11-2749-2018.pdf |
| spellingShingle | C. E. Stockwell C. E. Stockwell A. Kupc A. Kupc B. Witkowski B. Witkowski B. Witkowski R. K. Talukdar R. K. Talukdar Y. Liu V. Selimovic K. J. Zarzana K. J. Zarzana K. Sekimoto K. Sekimoto C. Warneke C. Warneke R. A. Washenfelder R. J. Yokelson A. M. Middlebrook J. M. Roberts Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument Atmospheric Measurement Techniques |
| title | Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| title_full | Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| title_fullStr | Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| title_full_unstemmed | Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| title_short | Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| title_sort | characterization of a catalyst based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument |
| url | https://www.atmos-meas-tech.net/11/2749/2018/amt-11-2749-2018.pdf |
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