Implications of the In‐Situ Measured Mass Absorption Cross Section of Organic Aerosols in Mexico City on the Atmospheric Energy Balance, Satellite Retrievals, and Photochemistry

Ammonia (NH3) is regarded as an important nitrogen oxides (NOx) precursor and also as an effective reductant for NOx removal in energy utilization through combustion, and it has recently become an attractive non-carbon alternative fuel. To have a better understanding of thermochemical properties of NH3, accurate in situ detection of NH3 in high temperature environments is desirable. Ultraviolet (UV) absorption spectroscopy is a feasible technique. To achieve quantitative measurements, spectrally resolved UV absorption cross-sections of NH3 in hot gas environments at different temperatures from 295 K to 590 K were experimentally measured for the first time. Based on the experimental results, vibrational constants of NH3 were determined and used for the calculation of the absorption cross-section of NH3 at high temperatures above 590 K using the PGOPHER software. The investigated UV spectra covered the range of wavelengths from 190 nm to 230 nm, where spectral structures of the [Formula: see text] transition of NH3 in the umbrella bending mode, v2, were recognized. The absorption cross-section was found to decrease at higher temperatures. For example, the absorption cross-section peak of the (6, 0) vibrational band of NH3 decreases from ∼2 × 10−17 to ∼0.5 × 10−17 cm2/molecule with the increase of temperature from 295 K to 1570 K. Using the obtained absorption cross-section, in situ nonintrusive quantification of NH3 in different hot gas environments was achieved with a detection limit varying from below 10 parts per million (ppm) to around 200 ppm as temperature increased from 295 K to 1570 K. The quantitative measurement was applied to an experimental investigation of NH3 combustion process. The concentrations of NH3 and nitric oxide (NO) in the post flame zone of NH3–methane (CH4)–air premixed flames at different equivalence ratios were measured.

Download Full-text

Black carbon over Mexico: the effect of atmospheric transport on mixing state, mass absorption cross-section, and BC/CO ratios

Atmospheric Chemistry and Physics ◽

10.5194/acp-10-219-2010 ◽

2010 ◽

Vol 10 (1) ◽

pp. 219-237 ◽

Cited By ~ 109

Author(s):

R. Subramanian ◽

G. L. Kok ◽

D. Baumgardner ◽

A. Clarke ◽

Y. Shinozuka ◽

...

Keyword(s):

Black Carbon ◽

Mexico City ◽

Cross Section ◽

Absorption Cross Section ◽

Atmospheric Transport ◽

Absorption Cross ◽

Air Masses ◽

Wet Scavenging ◽

The City ◽

Absorption Photometer

Abstract. A single particle soot photometer (SP2) was operated on the NCAR C-130 during the MIRAGE campaign (part of MILAGRO), sampling black carbon (BC) over Mexico. The highest BC concentrations were measured over Mexico City (sometimes as much as 2 μg/m3) and over hill-fires to the south of the city. The age of plumes outside of Mexico City was determined using a combination of HYSPLIT trajectories, WRF-FLEXPART modeling and CMET balloon tracks. As expected, older, diluted air masses had lower BC concentrations. A comparison of carbon monoxide (CO) and BC suggests a CO background of around 65 ppbv, and a background-corrected BC/COnet ratio of 2.89±0.89 (ng/m3-STP)/ppbv (average ± standard deviation). This ratio is similar for fresh emissions over Mexico City, as well as for aged airmasses. Comparison of light absorption measured with a particle soot absorption photometer (PSAP) and the SP2 BC suggests a BC mass-normalized absorption cross-section (MAC) of 10.9±2.1 m2/g at 660 nm (or 13.1 m2/g @ 550 nm, assuming MAC is inversely dependent on wavelength). This appears independent of aging and similar to the expected absorption cross-section for aged BC, but values, particularly in fresh emissions, could be biased high due to instrument artifacts. SP2-derived BC coating indicators show a prominent thinly-coated BC mode over the Mexico City Metropolitan Area (MCMA), while older air masses show both thinly-coated and thickly-coated BC. Some 2-day-old plumes do not show a prominent thickly-coated BC mode, possibly due to preferential wet scavenging of the likely-hydrophilic thickly-coated BC.

Download Full-text

Black carbon over Mexico: the effect of atmospheric transport on mixing state, mass absorption cross-section, and BC/CO ratios

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-9-9081-2009 ◽

2009 ◽

Vol 9 (2) ◽

pp. 9081-9115 ◽

Cited By ~ 2

Author(s):

R. Subramanian ◽

G. L. Kok ◽

D. Baumgardner ◽

A. Clarke ◽

Y. Shinozuka ◽

...

Keyword(s):

Black Carbon ◽

Mexico City ◽

Cross Section ◽

Absorption Cross Section ◽

Atmospheric Transport ◽

Absorption Cross ◽

Air Masses ◽

Atmospheric Processing ◽

The City ◽

Absorption Photometer

Abstract. A single particle soot photometer (SP2) was operated on the NCAR C-130 during the MIRAGE campaign (part of MILAGRO), sampling black carbon (BC) over Mexico. The highest BC concentrations were measured over Mexico City (sometimes as much as 2μg/m3) and over hill-fires to the south of the city. As expected, older, diluted air masses had lower BC concentrations. A comparison of carbon monoxide (CO) and BC suggests a CO background of around 65 ppbv, and a background-corrected BC/COnet ratio of 3.1 (ng/m3 STP)/ppbv (±25%). This ratio is similar for fresh emissions over Mexico City, as well as for aged airmasses. Comparison of light absorption measured with a particle soot absorption photometer (PSAP) and the SP2 BC suggests a BC mass-normalized absorption cross-section (MAC) of 10.3 m2g−1 (±30%) at 660 nm (or 12.4 m2g−1 @ 550 nm, assuming MAC is inversely dependent on wavelength). This appears independent of aging and similar to the expected absorption cross-section for aged BC, but values, particularly in fresh emissions, could be biased high due to instrument artifacts. SP2-derived BC coating indicators show a prominent thinly-coated BC mode over the Mexico City Metropolitan Area (MCMA), while older air masses show both thinly-coated and thickly-coated BC. BC mass per particle of the thinly-coated mode appears to increase as the air mass ages, possibly due to coagulation and/or increased coating of the particles containing smaller BC masses. Differences in the coating indicator patterns for similarly-aged air masses may be due to differences in atmospheric processing on each day, including mixing with non-MCMA air masses.

Download Full-text

Estimation of the mass absorption cross section of the organic carbon component of aerosols in the Mexico City Metropolitan Area (MCMA)

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-8-10189-2008 ◽

2008 ◽

Vol 8 (3) ◽

pp. 10189-10225 ◽

Cited By ~ 3

Author(s):

J. C. Barnard ◽

R. Volkamer ◽

E. I. Kassianov

Keyword(s):

Organic Carbon ◽

Black Carbon ◽

Mexico City ◽

Cross Section ◽

Light Absorption ◽

Absorption Cross Section ◽

Trace Gases ◽

Absorption Cross ◽

Enhanced Absorption ◽

Mass Absorption

Abstract. Data taken from the MCMA-2003 and the 2006 MILAGRO field campaigns are used to examine the absorption of solar radiation by the organic component of aerosols. Using irradiance data from a Multi-Filter Rotating Shadowband Radiometer (MFRSR) and an actinic flux spectroradiometer (SR), we derive aerosol single scattering albedo, π0,λ, as a function of wavelength, λ. We find that in the near-UV spectral range (250 to 400 nm) π0,λ is much lower compared to π0,λ at 500 nm indicating enhanced absorption in the near-UV range. Absorption by elemental carbon, dust, or gas cannot account for this enhanced absorption leaving the organic part of the aerosol as the only possible absorber. We use data from a surface deployed Aerodyne Aerosol Mass Spectrometer (AMS) along with the inferred π0,λ to estimate the Mass Absorption Cross section (MAC) for the organic carbon. We find that the MAC is about 10.5 m2/g at 300 nm and falls close to zero at about 500 nm; values that are roughly consistent with other estimates of organic carbon MAC. These MAC values can be considered as "radiatively correct" because when used in radiative transfer calculations the calculated irradiances/actinic fluxes match those measured at the wavelengths considered here. For an illustrative case study described here, we estimate that the light absorption by the "brown" (organic) carbonaceous aerosol can add about 40% to the light absorption of black carbon in Mexico City. This contribution will vary depending on the relative abundance of organic carbon relative to black carbon. Furthermore, our analysis indicates that organic aerosol would slow down photochemistry by selectively scavenging the light reaching the ground at those wavelengths that drive photochemical reactions. Finally, satellite retrievals of trace gases that are used to infer emissions currently assume that the MAC of organic carbon is zero. For trace gases that are retrieved using wavelengths shorter then 420 nm (i.e. SO2, HCHO, halogenoxides, NO2), the assumption of non-zero MAC values will induce an upward correction to the inferred emissions. This will be particularly relevant in polluted urban atmospheres and areas of biomass burning where organic aerosols are particularly abundant.

Download Full-text

Estimation of the mass absorption cross section of the organic carbon component of aerosols in the Mexico City Metropolitan Area

Atmospheric Chemistry and Physics ◽

10.5194/acp-8-6665-2008 ◽

2008 ◽

Vol 8 (22) ◽

pp. 6665-6679 ◽

Cited By ~ 117

Author(s):

J. C. Barnard ◽

R. Volkamer ◽

E. I. Kassianov

Keyword(s):

Organic Carbon ◽

Mexico City ◽

Cross Section ◽

Light Absorption ◽

Absorption Cross Section ◽

Trace Gases ◽

Organic Aerosol ◽

Absorption Cross ◽

Enhanced Absorption ◽

Carbon Component

Abstract. Data taken from the MCMA-2003 and the 2006 MILAGRO field campaigns are used to examine the absorption of solar radiation by the organic component of aerosols. Using irradiance data from a Multi-Filter Rotating Shadowband Radiometer (MFRSR) and an actinic flux spectroradiometer (SR), we derive aerosol single scattering albedo, ϖ0, λ, as a function of wavelength, λ. We find that in the near-UV spectral range (250 to 400 nm) ϖ0, λ is much lower compared to ϖ0, λ at 500 nm indicating enhanced absorption in the near-UV range. Absorption by elemental carbon, dust, or gas cannot account for this enhanced absorption leaving the organic carbon component of the aerosol (OA) as the most likely absorber. We use data from a surface deployed Aerodyne Aerosol Mass Spectrometer (AMS) along with the inferred ϖ0, λ to estimate the Mass Absorption Cross section (MAC) for the organic aerosol. We find that the MAC is about 10.5 m2/g at 300 nm and falls close to zero at about 500 nm; values that are roughly consistent with other estimates of organic aerosol MAC. These MAC values can be considered as "radiatively correct", because when used in radiative transfer calculations, the calculated irradiances/actinic fluxes match those measured at the wavelengths considered here. For an illustrative case study described here, we estimate that the light absorption by the "brown" (organic) carbonaceous aerosol can add about 40% to the light absorption of black carbon in Mexico City. This contribution will vary depending on the relative abundance of organic aerosol relative to black carbon. Furthermore, our analysis indicates that organic aerosol would slow down photochemistry by selectively scavenging the light reaching the ground at those wavelengths that drive photochemical reactions. Finally, satellite retrievals of trace gases that are used to infer emissions currently assume that the MAC of organic carbon is zero. For trace gases that are retrieved using wavelengths shorter then 420 nm (i.e. SO2, HCHO, halogenoxides, NO2), the assumption of non-zero MAC values will induce an upward correction to the inferred emissions. This assumption will be particularly relevant in polluted urban atmospheres and areas of biomass burning where organic aerosols are particularly abundant.

Download Full-text