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Title: Advanced Fine Particulate Characterization Methods

Abstract

The characterization and control of emissions from combustion sources are of significant importance in improving local and regional air quality. Such emissions include fine particulate matter, organic carbon compounds, and NO{sub x} and SO{sub 2} gases, along with mercury and other toxic metals. This project involved four activities including Further Development of Analytical Techniques for PM{sub 10} and PM{sub 2.5} Characterization and Source Apportionment and Management, Organic Carbonaceous Particulate and Metal Speciation for Source Apportionment Studies, Quantum Modeling, and High-Potassium Carbon Production with Biomass-Coal Blending. The key accomplishments included the development of improved automated methods to characterize the inorganic and organic components particulate matter. The methods involved the use of scanning electron microscopy and x-ray microanalysis for the inorganic fraction and a combination of extractive methods combined with near-edge x-ray absorption fine structure to characterize the organic fraction. These methods have direction application for source apportionment studies of PM because they provide detailed inorganic analysis along with total organic and elemental carbon (OC/EC) quantification. Quantum modeling using density functional theory (DFT) calculations was used to further elucidate a recently developed mechanistic model for mercury speciation in coal combustion systems and interactions on activated carbon. Reaction energies, enthalpies, free energies andmore » binding energies of Hg species to the prototype molecules were derived from the data obtained in these calculations. Bimolecular rate constants for the various elementary steps in the mechanism have been estimated using the hard-sphere collision theory approximation, and the results seem to indicate that extremely fast kinetics could be involved in these surface reactions. Activated carbon was produced from a blend of lignite coal from the Center Mine in North Dakota and sunflower hulls for the biomass material to be carbonized. The ability to remove mercury from a bituminous coal's derived flue gas was low. Removals of only 15% were attained while injecting 6 lb/Macf of activated carbon upstream of an electrostatic precipitator. Poisoning of sites on the activated carbon by SO{sub 2} and SO{sub 3} contributed to the poor mercury capture performance.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
University Of North Dakota
Sponsoring Org.:
USDOE
OSTI Identifier:
986864
DOE Contract Number:
FC26-98FT40320
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 09 BIOMASS FUELS; ABSORPTION; ACTIVATED CARBON; AIR QUALITY; BIOMASS; CARBON; CARBON COMPOUNDS; COAL; COMBUSTION; ELECTROSTATIC PRECIPITATORS; FINE STRUCTURE; FLUE GAS; FUNCTIONALS; GASES; KINETICS; LIGNITE; MERCURY; MICROANALYSIS; PARTICULATES; SCANNING ELECTRON MICROSCOPY

Citation Formats

Steven Benson, Lingbu Kong, Alexander Azenkeng, Jason Laumb, Robert Jensen, Edwin Olson, Jill MacKenzie, and A.M. Rokanuzzaman. Advanced Fine Particulate Characterization Methods. United States: N. p., 2007. Web. doi:10.2172/986864.
Steven Benson, Lingbu Kong, Alexander Azenkeng, Jason Laumb, Robert Jensen, Edwin Olson, Jill MacKenzie, & A.M. Rokanuzzaman. Advanced Fine Particulate Characterization Methods. United States. doi:10.2172/986864.
Steven Benson, Lingbu Kong, Alexander Azenkeng, Jason Laumb, Robert Jensen, Edwin Olson, Jill MacKenzie, and A.M. Rokanuzzaman. Wed . "Advanced Fine Particulate Characterization Methods". United States. doi:10.2172/986864. https://www.osti.gov/servlets/purl/986864.
@article{osti_986864,
title = {Advanced Fine Particulate Characterization Methods},
author = {Steven Benson and Lingbu Kong and Alexander Azenkeng and Jason Laumb and Robert Jensen and Edwin Olson and Jill MacKenzie and A.M. Rokanuzzaman},
abstractNote = {The characterization and control of emissions from combustion sources are of significant importance in improving local and regional air quality. Such emissions include fine particulate matter, organic carbon compounds, and NO{sub x} and SO{sub 2} gases, along with mercury and other toxic metals. This project involved four activities including Further Development of Analytical Techniques for PM{sub 10} and PM{sub 2.5} Characterization and Source Apportionment and Management, Organic Carbonaceous Particulate and Metal Speciation for Source Apportionment Studies, Quantum Modeling, and High-Potassium Carbon Production with Biomass-Coal Blending. The key accomplishments included the development of improved automated methods to characterize the inorganic and organic components particulate matter. The methods involved the use of scanning electron microscopy and x-ray microanalysis for the inorganic fraction and a combination of extractive methods combined with near-edge x-ray absorption fine structure to characterize the organic fraction. These methods have direction application for source apportionment studies of PM because they provide detailed inorganic analysis along with total organic and elemental carbon (OC/EC) quantification. Quantum modeling using density functional theory (DFT) calculations was used to further elucidate a recently developed mechanistic model for mercury speciation in coal combustion systems and interactions on activated carbon. Reaction energies, enthalpies, free energies and binding energies of Hg species to the prototype molecules were derived from the data obtained in these calculations. Bimolecular rate constants for the various elementary steps in the mechanism have been estimated using the hard-sphere collision theory approximation, and the results seem to indicate that extremely fast kinetics could be involved in these surface reactions. Activated carbon was produced from a blend of lignite coal from the Center Mine in North Dakota and sunflower hulls for the biomass material to be carbonized. The ability to remove mercury from a bituminous coal's derived flue gas was low. Removals of only 15% were attained while injecting 6 lb/Macf of activated carbon upstream of an electrostatic precipitator. Poisoning of sites on the activated carbon by SO{sub 2} and SO{sub 3} contributed to the poor mercury capture performance.},
doi = {10.2172/986864},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Jan 31 00:00:00 EST 2007},
month = {Wed Jan 31 00:00:00 EST 2007}
}

Technical Report:

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  • Particulate sampling experiments were carried out sampling both from a straight tube and from a continuous stirred tank reactor. Mathematical models for both were developed. Volume 2 is devoted to sampling from the stirred tank reactor; a different model was necessary. Thermophoresis was important with high temperature gradients; with fine particles (> 0.1 ..mu..m) Brownian diffusion and, at high concentrations, coagulation were important; for larger particles (> 1 ..mu..m) sedimentation was more important. (LTN)
  • Particulate sampling experiments were carried out sampling both from a straight tube and from a continuous stirred tank reactor. Mathematical models for both were developed. For the straight tube case: flow rate was important; sedimentation was important for particles > 5 ..mu..m in a horizontal pipe; thermophoresis was important if temperature gradients existed; Brownian motion, condensation and nucleation and coagulation were less important in the experimental conditions. For sampling from the stirred tank reactor, a different model was necessary. Thermophoresis was important with high temperature gradients; with fine particles (< 0.1 ..mu..m) Brownian diffusion and at high concentrations, coagulation weremore » important; for larger particles (> 1 ..mu..m) sedimentation was more important. (LTN)« less
  • This project was one of three collaborating grants designed to understand the atmospheric chemistry and aerosol particle microphysics impacting air quality in the Mexico City Metropolitan Area (MCMA) and its urban plume. The overall effort, titled MCMA- 2006, focused on: 1) the primary emissions of fine particles and precursor gases leading to photochemical production of atmospheric oxidants and secondary aerosol particles and 2) the measurement and analysis of secondary oxidants and secondary fine particular matter (PM) production, with particular emphasis on secondary organic aerosol (SOA). MCAM-2006 pursued it goals through three main activities: 1) performance and publication of detailed analysesmore » of extensive MCMA trace gas and fine PM measurements made by the collaborating groups and others during earlier MCMA field campaigns in 2002 and 2003; 2) deployment and utilization of extensive real-time trace gas and fine PM instrumentation at urban and downwind MCMA sites in support of the MAX-Mex/MILAGRO field measurements in March, 2006; and, 3) analyses of the 2006 MCMA data sets leading to further publications that are based on new data as well as insights from analysis and publication of the 2002/2003 field data. Thirteen archival publications were coauthored with other MCMA-2003 participants. Documented findings included a significantly improved speciated emissions inventory from on-road vehicles, a greatly enhanced understanding of the sources and atmospheric loadings of volatile organic compounds, a unique analysis of the high fraction of ambient formaldehyde from primary emission sources, a much more extensive knowledge of the composition, size distributions and atmospheric mass loadings of both primary and secondary fine PM, including the fact that the rate of MCMA SOA production greatly exceeded that predicted by current atmospheric models, and evaluations of significant errors that can arise from standard air quality monitors for ozone and nitrogen dioxide. Deployment of the Aerodyne mobile laboratory, equipped with instruments from five collaborating laboratories, at the T0 urban supersite, four downwind sites and the Tula industrial area yielded unique trace gas and fine PM data sets during the March 2006 MAXMex/MILAGRO campaign. In addition, on-road measurements as the mobile laboratory moved between sites provided extensive data on 2006 MCMA fleet averaged vehicle emissions. Analyses of 2006 data sets have yielded the identification of a close correlation between the rate of production of SOA and “Odd Oxygen” (O3 + NO2) and primary organic PM with CO in the MCMA urban plume, a more sophisticated understanding of the interplay between nitrogen oxide speciation and ozone production, the identification of significant vehicular emission sources of HCN and CH3CN (usually associated with biomass burning), characterization of the aging of primary carbonaceous PM, and updated 2006 MCMA fleet on-road trace gas and fine PM emissions. Results from analyses of 2002/2003 and 2006 emissions and ambient measurements have conveyed to Mexican air quality managers who are using these data to devise and assess air quality management strategies. All data sets and published analyses are available to DOE/ASP researchers evaluating the impact of urban emissions on regional climate.« less
  • This project was one of three collaborating grants funded by DOE/ASP to characterize the fine particulate matter (PM) and secondary PM precursors in the Mexico City Metropolitan Area (MCMA) during the MILAGRO Campaign. The overall effort of MCMA-2006, one of the four components, focused on i) examination of the primary emissions of fine particles and precursor gases leading to photochemical production of atmospheric oxidants and secondary aerosol particles; ii) measurement and analysis of secondary oxidants and secondary fine PM production, with particular emphasis on secondary organic aerosol (SOA), and iii) evaluation of the photochemical and meteorological processes characteristic of themore » Mexico City Basin. The collaborative teams pursued the goals through three main tasks: i) analyses of fine PM and secondary PM precursor gaseous species data taken during the MCMA-2002/2003 campaigns and preparation of publications; ii) planning of the MILAGRO Campaign and deployment of the instrument around the MCMA; and iii) analysis of MCMA-2006 data and publication preparation. The measurement phase of the MILAGRO Campaign was successfully completed in March 2006 with excellent participation from the international scientific community and outstanding cooperation from the Mexican government agencies and institutions. The project reported here was led by the Massachusetts Institute of Technology/Molina Center for Energy and the Environment (MIT/MCE2) team and coordinated with DOE/ASP-funded collaborators at Aerodyne Research Inc., University of Colorado at Boulder and Montana State University. Currently 24 papers documenting the findings from this project have been published. The results from the project have improved significantly our understanding of the meteorological and photochemical processes contributing to the formation of ozone, secondary aerosols and other pollutants. Key findings from the MCMA-2003 include a vastly improved speciated emissions inventory from on-road vehicles: the MCMA motor vehicles produce abundant amounts of primary PM, elemental carbon, particle-bound polycyclic aromatic hydrocarbons, carbon monoxide and a wide range of air toxics; the feasibility of using eddy covariance techniques to measure fluxes of volatile organic compounds in an urban core and a valuable tool for validating local emissions inventory; a much better understanding of the sources and atmospheric loadings of volatile organic compounds; the first spectroscopic detection of glyoxal in the atmosphere; a unique analysis of the high fraction of ambient formaldehyde from primary emission sources; characterization of ozone formation and its sensitivity to VOCs and NO x; a much more extensive knowledge of the composition, size distribution and atmospheric mass loadings of both primary and secondary fine PM, including the fact that the rate of MCMA SOA production greatly exceeded that predicted by current atmospheric models; evaluations of significant errors that can arise from standard air quality monitors for O 3 and NO 2; and the implementation of an innovative Markov Chain Monte Carlo method for inorganic aerosol modeling as a powerful tool to analyze aerosol data and predict gas phase concentrations where these are unavailable. During the MILAGRO Campaign the collaborative team utilized a combination of central fixed sites and a mobile laboratory deployed throughout the MCMA to representative urban and boundary sites to measure trace gases and fine particles. Analysis of the extensive 2006 data sets has confirmed the key findings from MCMA-2002/2003; additionally MCMA-2006 provided more detailed gas and aerosol chemistry and wider regional scale coverage. Key results include an updated 2006 emissions inventory; extension of the flux system to measure fluxes of fine particles; better understanding of the sources and apportionment of aerosols, including contribution from biomass burning and industrial sources; a comprehensive evaluation of metal containing particles in a complex urban environment; identification of a close correlation between the rate of production of SOA and “Odd Oxygen” (O 3 + NO 3) and primary organic PM with CO in the urban plume; a more sophisticated understanding of the relationship between ozone formation and ozone precursors: while ozone production in the urban area is VOC-limited, the response is mostly NOx-limited in the surrounding mountain. Comparison of the findings from 2003 and 2006 also confirm that the VOC levels have decreased during the three-year period, while NO x levels remain the same. The results from the 2002/2003 and 2006 have been presented at international conferences and communicated to Mexican government officials. In addition, a large number of graduate students and post-doctoral associates were involved in the project. All data sets and publications are available to the scientific community.« less