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Emission Factors of Hazardous Air Pollutants and Particulate Matter from the Pre-Harvest Burning of Florida Sugarcane

Permanent Link: http://ufdc.ufl.edu/UFE0041771/00001

Material Information

Title: Emission Factors of Hazardous Air Pollutants and Particulate Matter from the Pre-Harvest Burning of Florida Sugarcane
Physical Description: 1 online resource (102 p.)
Language: english
Creator: Hall, Danielle
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2010

Subjects

Subjects / Keywords: agricultural, air, biomass, burning, carbon, carbonyls, crop, elemental, emission, factor, hazardous, matter, organic, pahs, particulate, pollutants, sugarcane, toxics, vocs
Environmental Engineering Sciences -- Dissertations, Academic -- UF
Genre: Environmental Engineering Sciences thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: The pre-harvest burning of sugarcane is a common practice used to remove unwanted biomass prior to harvesting. Emission factors (EFs) for sugarcane pre-harvest burning are currently limited and are rated very low (category D) based on their reliability. The objective of this research was to investigate the emission factors of specific polycyclic aromatic hydrocarbons (PAHs), carbonyls, volatile organic compounds (VOCs) and particulate matter (PM2.5) from the pre-harvest burning of sugarcane. Additionally, the elemental carbon (EC) and organic carbon (OC) PM fractions were measured. An open burning combustion chamber was constructed to simulate field burning. For most experiments, dry sugarcane leaves were burned. A few experiments used whole sugarcane stalks, which exhibited higher moisture contents. The combustion efficiency was monitored to ensure that the combustion chamber accurately represented field burning. EPA sampling and analysis methods were employed to measure pollutants. PAHs were sampled using quartz filters and PUF/XAD-2 resin cartridges, followed by Soxhlet extraction and analysis by GC/MS. Carbonyls were collected using DNPH coated cartridges, extracted, and analyzed by HPLC. Gas samples were collected in Tedlar bags for subsequent analysis by GC/MS for VOC compounds. PM2.5 was sampled using a size selective cyclone, filter, and impinger train (for condensable particulate matter). EFs are comparable, but on the low end of EFs published for other types of biomass, which is likely due to the high combustion efficiency observed in this study. The total PAH EF was 7.13 and 8.18 mg/kg for dry and whole leaf experiments, respectively. Carbonyl EFs were 201 and 942 mg/kg for dry and whole leaf experiments, respectively. The total VOC EF (for BTEX and styrene compounds) was 23.9 mg/kg. In all compound classes, the low molecular weight compounds dominated emissions. The PM2.5 EF was 2.49 g/kg, and the OC and EC EFs were 0.23 and 0.80 g/kg, respectively. The results of this project provide the most accurate data available about the EFs of air toxics released during the pre-harvest burning of Florida sugarcane. With more reliable data, the current EFs can be validated and expanded. Subsequently, regulating agencies can more accurately determine human and environmental exposure and therefore make better management and permitting decisions.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Danielle Hall.
Thesis: Thesis (M.E.)--University of Florida, 2010.
Local: Adviser: Wu, Chang-Yu.
Electronic Access: RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2012-04-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2010
System ID: UFE0041771:00001

Permanent Link: http://ufdc.ufl.edu/UFE0041771/00001

Material Information

Title: Emission Factors of Hazardous Air Pollutants and Particulate Matter from the Pre-Harvest Burning of Florida Sugarcane
Physical Description: 1 online resource (102 p.)
Language: english
Creator: Hall, Danielle
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2010

Subjects

Subjects / Keywords: agricultural, air, biomass, burning, carbon, carbonyls, crop, elemental, emission, factor, hazardous, matter, organic, pahs, particulate, pollutants, sugarcane, toxics, vocs
Environmental Engineering Sciences -- Dissertations, Academic -- UF
Genre: Environmental Engineering Sciences thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: The pre-harvest burning of sugarcane is a common practice used to remove unwanted biomass prior to harvesting. Emission factors (EFs) for sugarcane pre-harvest burning are currently limited and are rated very low (category D) based on their reliability. The objective of this research was to investigate the emission factors of specific polycyclic aromatic hydrocarbons (PAHs), carbonyls, volatile organic compounds (VOCs) and particulate matter (PM2.5) from the pre-harvest burning of sugarcane. Additionally, the elemental carbon (EC) and organic carbon (OC) PM fractions were measured. An open burning combustion chamber was constructed to simulate field burning. For most experiments, dry sugarcane leaves were burned. A few experiments used whole sugarcane stalks, which exhibited higher moisture contents. The combustion efficiency was monitored to ensure that the combustion chamber accurately represented field burning. EPA sampling and analysis methods were employed to measure pollutants. PAHs were sampled using quartz filters and PUF/XAD-2 resin cartridges, followed by Soxhlet extraction and analysis by GC/MS. Carbonyls were collected using DNPH coated cartridges, extracted, and analyzed by HPLC. Gas samples were collected in Tedlar bags for subsequent analysis by GC/MS for VOC compounds. PM2.5 was sampled using a size selective cyclone, filter, and impinger train (for condensable particulate matter). EFs are comparable, but on the low end of EFs published for other types of biomass, which is likely due to the high combustion efficiency observed in this study. The total PAH EF was 7.13 and 8.18 mg/kg for dry and whole leaf experiments, respectively. Carbonyl EFs were 201 and 942 mg/kg for dry and whole leaf experiments, respectively. The total VOC EF (for BTEX and styrene compounds) was 23.9 mg/kg. In all compound classes, the low molecular weight compounds dominated emissions. The PM2.5 EF was 2.49 g/kg, and the OC and EC EFs were 0.23 and 0.80 g/kg, respectively. The results of this project provide the most accurate data available about the EFs of air toxics released during the pre-harvest burning of Florida sugarcane. With more reliable data, the current EFs can be validated and expanded. Subsequently, regulating agencies can more accurately determine human and environmental exposure and therefore make better management and permitting decisions.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Danielle Hall.
Thesis: Thesis (M.E.)--University of Florida, 2010.
Local: Adviser: Wu, Chang-Yu.
Electronic Access: RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2012-04-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2010
System ID: UFE0041771:00001


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1 EMISSION FACTORS OF HAZARDOUS AIR POLLUTANTS AND PARTICULATE MATTER FROM THE PRE-HARVEST BU RNING OF FLORIDA SUGARCANE By DANIELLE HALL A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING UNIVERSITY OF FLORIDA 2010

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2 2010 Danielle Hall

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3 To my grandparents, Ken Bayless and Const ance & Marshall Hall, and my parents, Tim & Jennifer Hall, who have given me courage, inspiration, and freedom to push boundaries and achieve this milestone

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4 ACKNOWLEDGMENTS First and foremost, I would like to thank my research advisor, Dr. Wu, for his inspiration, hard work and guidance. Dr. Wus energetic and positiv e attitude for learning is inspiring to every student. I am thankful for the countless hours he spent helping me write papers and solve research problem s, while also giving me the creative freedom to develop my problem solving and thinking skills. I would also like to thank my committee, Dr. Hsu, Dr. Delfino, and Dr. Ilacqua, for providing me important guidance in my research endeavors. I am espe cially grateful to Dr. Hsu, my research mentor, for her hard work in developi ng this research project and for teaching me so many valuable things. I would like to acknowledge the funding ag ency for this projectthe Palm Beach County Health Department as well as G uenter Engling (Research Center for Environmental Sciences, Academia Sinica, Taipei, Taiwan) for performing the EC/OC analysis. I am very grateful for my research team, past and presentJun Wang, Kuei-Min Yu, Nate Topham, Krisha Capeto, Mark Kalivoda, Scott Brown, Lea Ramkellawan, and Heather Waters whom spent countless hours helping me perform experiments, which was always hard workphysically and mentally I am also thankful for the patience and support my fellow lab mates have shown me. I would like to thank my parents fo r their constant love and support, and particularly for all my Dads technical support building and fixing thin gs for my project. Last, but not least, I would like to thank all my friends who have always been there to help me through stressful times and revive me!

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5 TABLE OF CONTENTS page ACKNOWLEDG MENTS .................................................................................................. 4 LIST OF TABLES............................................................................................................ 7 LIST OF FIGURES .......................................................................................................... 9 LIST OF ABBR EVIATIONS ........................................................................................... 10 ABSTRACT................................................................................................................... 12 CHA PTER 1 INTRODUCTION.................................................................................................... 14 Significance of Sugarcane Pre-Harvest Burning ..................................................... 14 Biomass Burning Em ission Fa ctors ........................................................................ 15 Emission Factors for Sugarcane Bu rning ................................................................ 22 Health and Environmental Impacts from Sugarcane Fi eld Burning ......................... 23 Research Ob jective ................................................................................................ 24 2 EXPERIMENTAL METHODOLOGY ....................................................................... 26 Summary of Experim ental A pproach ...................................................................... 26 Combustion C hamber De sign ................................................................................. 26 Experimental Procedur es ........................................................................................ 27 Uniformity Test ........................................................................................................ 29 Polycyclic Aromatic Hydroc arbons .......................................................................... 29 Sampli ng.......................................................................................................... 30 Analys is............................................................................................................ 30 QA/QC.............................................................................................................. 31 Carbony ls................................................................................................................ 32 Sampli ng.......................................................................................................... 32 Analys is............................................................................................................ 32 QA/QC.............................................................................................................. 33 Volatile Or ganic Co m pounds.................................................................................. 33 Sampli ng.......................................................................................................... 33 Analys is............................................................................................................ 34 QA/QC.............................................................................................................. 34 PM2.5....................................................................................................................... 35 Sampli ng.......................................................................................................... 35 Analys is............................................................................................................ 36 QA/QC.............................................................................................................. 38 Flue Ga ses ............................................................................................................. 38

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6 Temperature and Pre ssure ..................................................................................... 40 EF Calcul ation ........................................................................................................ 41 3 RESULT S............................................................................................................... 47 Uniformity Test ........................................................................................................ 47 Flue Ga ses ............................................................................................................. 47 PAHs....................................................................................................................... 48 Test 1 (5 /14/09)................................................................................................ 49 Test 2 (5 /27/09)................................................................................................ 49 Tests 3-4 (6/12/09)........................................................................................... 49 Test 5 (1 /27/10)................................................................................................ 50 Carbony ls................................................................................................................ 50 Test 1 (3 /31/09)................................................................................................ 50 Tests 2-4 (5/28/09)........................................................................................... 51 Test 5 ( 12/13/ 09) .............................................................................................. 51 VOCs...................................................................................................................... 51 Tests 1 & 2 (6/1/09) .......................................................................................... 52 Tests 3 & 4 (9/29/09) ........................................................................................ 52 Recovery Study ................................................................................................ 53 PM2.5....................................................................................................................... 53 Mass EF s......................................................................................................... 53 EC and OC EFs ................................................................................................ 54 4 DISCUSSION......................................................................................................... 71 EF summary........................................................................................................... 71 PAHs....................................................................................................................... 71 Carbony ls................................................................................................................ 74 VOCs...................................................................................................................... 76 PM2.5....................................................................................................................... 77 EC and OC ............................................................................................................. 78 HAP Emission Estimates ........................................................................................ 80 5 SUMMARY AND CO NCLUSIONS .......................................................................... 94 LIST OF RE FERENCES ............................................................................................... 96 BIOGRAPHICAL SKETCH .......................................................................................... 102

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7 LIST OF TABLES Table Page 1-1 Published AP-42 EFs for sugar ca ne pre-harvest burning)................................. 25 2-1 Gas analyzer summary ....................................................................................... 41 3-1 PAH experiment sa mp ling cond itions................................................................. 55 3-2 Test 1 PAH concentrati ons and EFs .................................................................. 55 3-3 Test 1 QA /QC results ......................................................................................... 56 3-4 Test 2 PAH conc entrations and EFs ................................................................... 56 3-5 Test 2 QA /QC results ......................................................................................... 57 3-6 Tests 3 and 4 PAH co ncentration s and EFs ....................................................... 58 3-7 Tests 3 and 4 QA/QC results.............................................................................. 59 3-8 Test 5 PAH conc entrations and EFs ................................................................... 60 3-9 Test 5 QA /QC results ......................................................................................... 61 3-10 Carbonyl experi ment samplin g condit ions.......................................................... 62 3-11 Test 1 carbonyl concentrations and EFs ............................................................ 62 3-12 Tests 2,3,4 carbonyl concentration s and EFs ..................................................... 63 3-13 Test 5 carbony l concentrati ons and EFs ............................................................ 64 3-14 VOC experime nt sampling conditi ons ................................................................ 64 3-15 Tests 1 and 2 VO C concentrati ons and EFs ...................................................... 65 3-16 Tests 1 and 2 LCS % re coveri es ........................................................................ 65 3-17 Tests 3 and 4 VOC c oncentration s and EFs ...................................................... 66 3-18 Tests 3 and 4 LC S % recoveries ........................................................................ 66 3-19 Recovery st udy results ....................................................................................... 67 3-20 PM experiment samp ling cond itions................................................................... 67 3-21 PM concentra tions and EFs................................................................................ 68

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8 3-22 EC/OC experiment sampling co nditions ............................................................. 68 3-23 OC and EC conc entrations and EFs ................................................................... 69 4-1 EF summary ....................................................................................................... 81 4-2 Signature PAH compound ratios ........................................................................ 82 4-3 VOC EF (mg/k g) co mparison.............................................................................. 83 4-4 PM EF (g/k g) com parison ................................................................................... 83 4-5 EC and OC EF compar ison ................................................................................ 83 4-6 Emission factors and yearly emissions for sugarcane field burning .................... 84 4-7 Contribution of sugarcane field bu rning to annual emis sions in PBC and Florid a................................................................................................................ 85

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9 LIST OF FIGURES Figure Page 1-1 Florida sugarc ane field burning .......................................................................... 25 2-1 Combusti on chamber ......................................................................................... 42 2-2 PAH compound struct ures .................................................................................. 43 2-3 PAH samp ling train ............................................................................................. 44 2-4 Carbonyl sa mpling tr ain ...................................................................................... 44 2-5 Tedlar bag contai ned in VacU-Cham ber ........................................................... 45 2-6 PM2.5 sampling train........................................................................................... 45 2-7 Pressure and temperat ure measu rem ent points................................................. 46 3-1 Uniformity test data ............................................................................................. 69 3-2 Flue gas concent rations and MCE ...................................................................... 70 4-1 Comparison of PAH EFs to Jenkins et al., 1996b ............................................... 86 4-2 Comparison of PAH EFs to Hays et al ., 2002 ..................................................... 87 4-3 Total PAH concentration as a func tion of individual PAH concentrations ........... 88 4-4 Total PAH EF as a func tion of individual PAH EFs ............................................. 89 4-5 Total carbonyl EF as a func tion of individual carbony l EFs ................................ 90 4-6 Total carbonyl concentration as a function of individual c arbonyl concentra tion...................................................................................................... 91 4-7 Comparison of carbony l EFs .............................................................................. 92 4-8 Comparison of VOC E Fs.................................................................................... 93

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10 LIST OF ABBREVIATIONS CAS Columbia Analytical Services CCN Cloud condensation nuclei CE Combustion efficiency CPM Condensable particulate matter DGM Dry gas meter DI Deionized DLCS Duplicate laborat ory control sample DNPH 2,3-dinitrophenylhydrazine EF Emission factor EC Elemental carbon GC Gas chromatography HAP Hazardous Air Pollutant HPLC High performance liquid chromatography IMPROVE Interagency monitoring of protected visual environments FID Flame ionization detection LCS Laboratory control sample MC Moisture content MCE Modified combustion efficiency MRL Minimum report limit MS Mass spectrometry NA Not applicable NATA National air toxics assessment NIOSH National Institute for O ccupational Safety and Health OC Organic carbon

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11 OTM Other test method PAH Polycyclic aromatic hydrocarbon PBC Palm Beach County PCDD Polychlorinated dibenzo-p-dioxin PCDF Polychlorinated dibenzo-p-furan PM Particulate matter QA Quality assurance QAPP Quality assurance project plan QC Quality control Scfm Standard cubic feet per minute TEQ Toxic equivalents USEPA United States Environmental Protection Agency VOC Volatile organic compound

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12 Abstract of Thesis Pres ented to the Graduate School of the University of Florida in Partial Fulf illment of the Requirements for t he Degree of Master of Engineering EMISSION FACTORS OF HAZARDOUS AIR POLLUTANTS AND PARTICULATE MATTER FROM THE PRE-HARVEST BU RNING OF FLORIDA SUGARCANE By Danielle Hall May 2010 Chair: Chang-Yu Wu Major: Environmental Engineering Sciences The pre-harvest burning of sugarcane is a common practice used to remove unwanted biomass prior to harvesting. Emission factors (EFs) for sugarcane preharvest burning are currently limited and are rated very low (category D) based on their reliability. The objective of this research was to investigate the emission factors of specific polycyclic aromatic hydrocarbons (PAHs), carbonyls, volatile organic compounds (VOCs) and par ticulate matter (PM2.5) from the pre-harvest burning of sugarcane. Additionally, the elemental carbon (EC) and organic carbon (OC) PM fractions were measured. An open burning combustion chamber was c onstructed to simulate field burning. For most experiments, dry sugarcane leaves were burned. A few experiments used whole sugarcane stalks, which exhibited high er moisture contents. The combustion efficiency was monitored to ensure that the combustion chamber accurately represented field burning. EPA sampling and analysis methods were employed to measure pollutants. PAHs were sampled using quartz filters and PUF/ XAD-2 resin cartridges, followed by Soxhlet

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13 extraction and analysis by GC/MS. Carbony ls were collected using DNPH coated cartridges, extracted, and analyzed by HPLC. Gas samples were collected in Tedlar bags for subsequent analysis by GC/MS for VOC compounds. PM2.5 was sampled using a size selective cyclone, filter, and impinger train (for condensable particulate matter). EFs are comparable, but on the low end of EFs published for other types of biomass, which is likely due to the high com bustion efficiency observed in this study. The total PAH EF was 7.13 0.94 and 8.18 3.26 mg/kg for dry and whole leaf experiments, respectively. Carbonyl EFs are 201 38.2 and 942 539 mg/kg for dry and whole leaf experiments, respectively. The total VOC EF (for BTEX and styrene compounds) is 23.9 2.62 mg/kg. In all compound cla sses, the low molecular weight compounds dominated emissions. The PM2.5 EF was 2.49 0.66 g/kg, and the OC and EC EFs were 0.23 0.102 and 0.80 0.115 g/kg, respectively. The results of this project provide the most accurate data available about the EFs of air toxics released during the pre-harvest burning of Florida sugarcane. With more reliable data, the current EFs can be valid ated and expanded. Subsequently, regulating agencies can more accurately determine human and environmental exposure and therefore make better management and permitting decisions.

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14 CHAPTER 1 INTRODUCTION Significance of Sugarcane Pre-Harvest Burning In 2008, 868,000 acres of sugarcane were harvested in the United States. Louis iana and Florida are the largest s ugarcane producing stat es, each harvesting 405,000 and 401,000 acres, respectively in 2008 (National Agricultural Statistics Service, 2009). The remainder of sugarcane is grown in Texas and Hawaii. In Florida, sugarcane agriculture is concentrated in Palm Beach County (PBC) and surrounding areas in the Lake Okeechobee agricultural area. Prescribed burning of sugarcane fields is practiced to facilitate harvesting by quickly and cheaply removing unwanted biomass (leaf trash), to reduce dangers from snakes and insects (Gullett et al., 2006), and to increase the sugar content of the stalk by water evaporation (Zamperlini et al., 2000) Figure 1-1 shows pictures of Florida sugarcane fields being burned. Due to the dry and densely packed nature of the sugarcane, field burning is a quick and intense processa 40-acre plot will burn in 15 to 20 minutes. In Florida, fields are burned on a plot-by-plot basis (permitted through the Division of Forestry) when climatic conditions are favorable such that smoke plumes will not impact major roadways or densely popula ted areas. Fields are burned only during the harvest season that, in Florida, extends from October to April. Emission factors (EFs) quantify the amount of a pollutant released per unit mass burned and are used to develop pollutant emission inventorie s, which allow regulators to asses contributions from sources on local, regional, and global scales. EFs are also used as inputs for atmospheric dispersi on models. Knowing the detailed chemical characterization of emissions can also be useful for source apportionment studies,

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15 which attempt to assign air pollutant emissi ons to their respective sources based on unique chemical signatures (Dhammapala et al ., 2007a; Hays et al., 2002; Liu et al., 2008; Turn et al., 1997; Zheng et al., 2002). Current EFs for sugarcane pre-harvest bur ning, published by t he United States Environmental Protection Agency (US EPA), are rated D on a scale from A to E indicating they are based on a limited data set and thus, are unreliable (US EPA, 1995). The EFs are based on only one study of Hawaiian sugarcane and there is reason to believe other types of sugarcane could diffe r significantly (Gullet et al., 2006). In addition, only EFs for total particulate matter (PM), CO, and hydrocarbons exist. There are no compound-specific EFs for hazardous air pollutants (HAPs) such as polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs) or carbonyls. According to the 2006 PBC emissions inventor y, the practice of sugarcane pre-harvest burning contributes to 17% of VOC emi ssions, 16% of CO emission and 45% of particulate matter emissions in PBC, highlig hting the important c ontribution of this practice to the local emission inventor y of PBC (Palm Beach County Health Department, 2006). Biomass Burning Emission Factors Biomass burning enc ompasses a wide range of combustion activities including: wildfires, prescribed burning, agricultural bur ning, and biofuel combustion in stoves for cooking and heating. These burning activi ties have been identified as a significant source of atmospheric emissions that pose si gnificant health risks as well as contribute to local, regional, and global air quality degradation (Jenkins et al., 1996b; Lemieux et al., 2004; Langmann et al., 2009; Turn et al., 1997). Common pollutants released

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16 include: aerosols; gaseous compounds such as VOCs, carbonyls, greenhouse gases; and semi-volatile compounds like PAHs. Many of the organic compounds (i.e., PAHs, carbonyls and VOCs) that are produced from the pyrolysis of the biomass have known or suspected toxic and carcinogenic effects and are classified as HAPs. Carbonyl and VOC emissions are also of environmental concern because of the important role they play in photochemical smog processes and secondary organic aerosol fo rmation (Hays et al., 2002; Liu et al., 2008; Na and Cocker, 2008; Tsai et al., 2003; Wei et al., 2008; Zhang and Smith, 1999). Elevated PM concentrations have been linke d to increased morbidity and mortality and can contribute to decreased lung function (i.e., coughing, wheezing, asthma attacks), as well as cardiovascular diseases and lung cancer. (Mitra et al., 2002; Pedersen et al., 2005; Russell and Br unekreef, 2009). Particles generated through biomass combustion are often less than 1 m (aerodynamic diameter), which are particularly harmful to human health since t hey can travel deep into the respiratory system (Jenkins et al, 1996a). Particles of this size are also of special concern because they contain a major fraction of adsorbed ai r toxics such as PAHs (Mitra et al., 2002; Pedersen et al., 2005). PM also has significant atmospheric and environmental impacts, which are largely related to its characteristics (i.e., size and composition). PM from biomass burning is mainly carbonaceous, consisting of element al carbon (EC) and organic carbon (OC) (Dhammapala et al., 2007a; McMeeking et al., 2009; Na and Cocker, 2008). The fractions of EC and OC are very important in characterizing the impacts of PM, since they have very different effectsEC absor bs solar radiation and has a heating effect,

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17 whereas OC scatters radiation and cools the atmosphere. T he relative contribution of EC compared to OC can also be a useful marker for different types of combustion sources (Habib et al., 2008, Zheng et al., 2002) PM can also affect the hydrological cycl e due to its role in cloud formation and microphysical processes. Generally PM acts as cloud condensation nuclei (CCN), which increases cloud cover and rain forma tion. However, some studies have suggested that the CCN produced from biomass combustion processes, such as sugarcane burning, are so small that they effectively prevent the coalescence of rain, thereby decreasing rainfall (Crutzen and Andr eae, 1990; Lara et al., 2005; Twomey and Warner, 1967; Warner, 1968). Biomass combustion is a complex process characterized by numerous burning phases, which will exhibit a variety of EF s. There are two major burning phases flaming and smoldering, whic h can be distinguished by their combustion efficiencies (CEs). Flaming combustion exhibits a high CE, emitting CO2 as the main product. Smoldering combustion is a lower temperature oxidation process and occurs when there is limited oxygen suppl y. The smoldering stage exhibits a lower CE and higher emissions of CO and other incomplete combustion products. The contributions from flaming and smoldering in the overall fire event are highly variable and depend on the fire intensity, fuel density, and fuel moistu re among other factors. Pollutant emissions are a strong function of the CE, since they form as a resu lt of incomplete combustion (Langmann et al., 2009; Tissari et al., 2008; Ward and Hardy, 1991). A number of studies have been conducted in order to better estimate the emissions from biomass burning. Generally laboratory studies, which use chambers to

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18 simulate burning, are preferred because of the ease in controlling variables; however, laboratory studies are often criticized for their inability to accurately model field burning conditions. Although laboratory studies ma y not replicate the complex conditions encountered in the field, they are useful to control variables and replicate burning conditions from experiment to experiment. L aboratory studies also provide information about the entire fire process because the sa mpled emissions are well mixed over the entire burning process, whereas field samp les may be inclined toward flaming or smoldering combustion depending on the sampling location (Chen et al., 2007; Dhammapala et al., 2007b; McMeeking et al., 2009). Jenkins et al. (1996a) performed a compr ehensive study of the EFs of various pollutants from crop and forest residues commonly burned in California. They conducted controlled laboratory simulations in a combustion wind tunnel designed to mimic field conditions. The wind tunnel allo wed combustion of a relatively large amount of mass, while also controlling wind speeds in order to simulate different field conditions (i.e, pile fires vs. spreading fires). CO, CO2, NOx, SO2, hydrocarbons, PM, VOCs and PAHs emissions were measured and EFs were developed. In general, emissions from each fuel source were sim ilar and it was observed that emissions were less dependent on fuel type compared to burni ng conditions (i.e. wind speed, fuel loading, burning intensity and combusti on efficiency). Generally, PAH emissions increased with a lighter fuel loading and increased wind speeds, which led to a weaker flame structure and lower combustion efficienc ies. VOC emissions were more variable between the fuel types with emissions from Douglas Fir and Ponderosa Pine being high in comparison to the other fuel types.

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19 Hays et al. (2002) investi gated gas-phase and particle emissions from foliar fuels typically burned in U.S. wildfires using a large burn enclosure. The fuels were arranged to mimic field conditions in view of the mo isture content (MC), fuel density, and airflow characteristics. PM2.5 EFs ranged from 10.8 3.9 g/kg to 33.5 10.5 g/kg and the PM was composed mainly of OC (>80%). The ratio of partitioning between gas-phase to particle-phase PAH emissions ranged from 3:1 to 27:1. Fuels with the highest PAH concentrations in the particulate phase exhi bited longer smoldering stages caused by moister and less densely packed fuelsthese conditions led to lower CEs and thus higher PAH emissions. Benzene and tol uene were the most abundant aromatic hydrocarbons. The 10 hydrocarbons listed as HAPs comprised 18 wt % of the 78 hydrocarbons quantified. Low molecular weight compounds, such as formaldehyde and acetaldehyde, dominated carbonyl emission s and HAP carbonyl compounds comprised 30 wt % of carbonyl emissions. Hays et al. (2005) investi gated the physical and chemical characteristics of PM emissions from wheat and rice agricultural residues in a si milar manner as Hays et al. (2002). PM2.5 EFs were 4.71 0.04 g/kg and 12.95 0.3 g/kg for wheat and rice fuels, respectively. These EFs are lower than t he EFs determined by Hays et al. (2002) for wildfire foliar fuels tested in the same combustion enclosure. The differences were attributed to different burning conditions. Specifically, the foliar fuels were moister than the agricultural materials, and higher MCs may inhibit complete combustion. PM was principally carbonaceous in nature with high OC to EC ratios. Using the EFs for PM2.5 obtained in this study, the researchers estimated that wheat stubble burning could account for approximately 15% of anthropogenic PM2.5 emissions in Washington and

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20 6% of US emissions. On the other hand, rice stubble burning is estimated to contribute to only 1.5% to the U.S. PM2.5 inventory, but may be a majo r global emission source considering the widespread practice of rice stubble burning around the world. PM2.5 emissions from wheat and Kentu cky bluegrass stubble burning were investigated in correlation with the CE by Dh ammapala et al. (2006) in a U.S. EPA test burn facility. PM emissions were observed to increase with decreasing CEPM EFs for wheat stubble were 0.8 0.4 g/kg and 4.7 0.4 g//kg for CEs of 98% and 92%, respectively. Kentucky bluegrass burning exhibited a PM2.5 EF of 12.1 1.4 g/kg with an average CE of 90%. Dhammapala et al. (2007a) measur ed EFs for PAHs, methoxyphenols, levoglucosan, EC and OC from wheat and K entucky bluegrass in the same burn facility as Dhammapala et al. (2006). Particulat e and gaseous PAH emissions were quantified separately, and emissions were predominantly in the gas phase% for wheat emissions and 70% for bluegrass emissions Lower molecular weight compounds dominated the emissions with acenaphthylene and phenanthrene being the most abundant compounds. The PM mass was dom inated by EC and OCapproximately 63% for both wheat and bluegrass. OC emi ssions were higher than EC emissions, and both the EC and OC emissions decreased with increasing CE. To investigate the differences in EFs deriv ed from simulated ex periments and field experiments, Dhammapala et al. ( 2007b) conducted field sampling for PM2.5, CO, and PAH emissions from Kentucky bluegrass and wheat stubble burning and compared the EFs to their previous labor atory experiments (Dhammapala et al. 2006, Dhammapala et al. 2007a). The researchers found reasonable agreement between EFs derived from

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21 field studies compared to laboratory studies at combustion efficiencies greater than 90%. They concluded that EFs from fi eld and simulated burn experiments will have some differences because of the inherent differences in the situations; however, simulated experiments can provide accurate estimates if the simulated conditions closely mimic the field condition s, for example, the CE. A large experimental campaign is being co nducted at the U.S. Forest Services Missoula Fire Science Laboratory to charac terize smoke emissions from numerous fuels commonly burned in U.S. wildfires as we ll as a few agricultural fuels, including sugarcane. Physical, chemical, and optical properties of emissions are being studied in order to better understand wildland and pre scribed burning effects on visibility impairment and PM inventories. In these studies a comp rehensive profile of gaseous and PM emissions has been reported for a variety of fuels (Carrico et al., 2008; Chen et al., 2007; McMeeking, 2009). Yokels on et al. (2008) reported a PM2.5 EF for sugarcane as 2.17 g/kg as well as EFs for other VOC compounds. Having a more comprehensive understanding of emission characteristics and influencing factors aids in better predictions of biomass burning on emission inventories, visib ility, and radiation budgets. From previous studies it has been estab lished that pollutant emissions are a strong function of the CE and ar e influenced by a number of va riables. Factors that will have significant impacts on the EFs incl ude meteorology, biomass condition (MC, loading density, pesticide/fertilizer app lication), burning technique, and fire characteristics (temperature ventilation, spreading rate, intensity, turbulence) (Dhammapala et al., 2007a; Jenkins et al., 1996a; Lu et al., 2009).

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22 Emission Factors for Sugarcane Burning The current EFs factors, published in AP-42, for sugarcane burnin g were developed by E.F. Darley and S.L. Lerman (1975) at the Un iversity of California, Riverside. In this study, sugarcane plant mate rial (collected from fi elds in Hawaii) was combusted in a burning tower. PM (total ), CO, hydrocarbon and trace metal emissions were measured. EFs determined by this study are summarized in Table 1-1. The particle size distribution was also measured% of particles were below 0.5 m and less than 2% were greater than 2 m, demonstrating that most PM is in the fine particle size range. Meyer et al. (2004) studied t he EFs of polychlorinated dibenzop -dioxins (PCDDs) and furans (PCDFs) from Australian s ugarcane using both field and laboratory experiments. The researcher s found very different EFs for the laboratory and field experiments.7 to 20 pg toxic equivalent s (TEQ) per gram of carbon for laboratory experiments compared to 1.2 and 2.9 pg TEQ per gram of carbon in field experiments. They also found differences in the congener and homologue profiles of the PCDD and PCDF compounds between experiment types. PCDFs dominated the emissions in the laboratory experiments, but had much lower contributions in field experiments. The researches linked the discrepancies to the differences in residence time at high temperatures, which is required for dioxin syn thesis. In field burning, emissions rapidly rise and are cooled from dilution with ambient air; however, emissions in this laboratory experiment remained at higher temperatur es longer, thus further supporting dioxin formation.

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23 Gullett et al. (2006) investigated the EFs of PCDDs and PCDFs from Floridian and Hawaiian sugarcane burning us ing an open burn combustion facility. The two types of sugarcane exhibited very different EFs. The Hawaiian sugarcane had an average EF of 253 ng TEQ per kg of carbon burned (kgCb) whereas the Florida sugarcane had EFs of 25 ng TEQ/kgCb and 5 ng TEQ/kgCb. The researchers speculated that the large difference in EFs was due to the different treatment (fertilizer and pesticide use) and location (affects from sea breezes) of t he sugarcane. Chlorine was found to be 13 times higher in Hawaiian cane than in Florida cane, due to the use of KCl by Hawaiian growers and from ocean winds laden with salt. Based on this study, it was estimated that sugarcane burning contri buted to 15% of the PCDD and PCDF inventory for the US in 2000, a large contribution of these harmful compounds. Health and Environmental Impact s from S ugarcane Field Burning In Brazil, numerous studies have been cond ucted on the health and environmental impacts of sugarcane burning. Lara et al. (2005) used prin cipal component analysis to study the properties of aerosols from sugar cane burning and to assess their contribution to ambient particle concentrations in Piraci caba, Brazil. They concluded that sugarcane fires were the largest source of particulate matter in the areaspecifically, 60% of the fine mode (PM2.5) mass of PM and 25% of the coarse mode (PM2.5-10) mass of PM. In another study by Kirchhoff et al. (1991), am bient concentrations of CO and ozone (O3) were observed to be elevated during sugarcane burning periods in Sau Paulo, Brazil. Due to negative environmental and health impacts associated wit h sugarcane burning, more than 100 sugarcane producers in Sau Paul o, Brazil have agreed to stop the practice of pre-harvest burning by 2017. Instead, fields will be manually harvested and the biomass will be used in cogeneration electric power plants (Reuters, 2007).

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24 Rogge et al. (1997) compared the composition and size di stribution of particulate matter from two sites in PBC, Florida wher e the majority of Florida sugarcane is cultivated. Belle Glade is a rural site dominated by agricul ture, particularly sugarcane. Delray Beach is an urban site with numerous industries including electric power production, construction, aircraft testing, computer and electronics manufacturing, waste incineration, and concrete and asphalt produ ction. Belle Glade and Delray Beach showed very similar PM10 concentrations from April to September; however, from October to March (during the sugar cane burning season), the average PM10 and PM2.5 concentrations were 25% and 28.5% higher, re spectively, in Belle Glade than Delray Beach. In addition, ambient PAH concentrations in Belle Glade were 20 times higher in January compared to May suggesting the in fluence of sugarcane pre-harvest burning on the ambient air quality. T he ambient PAH concentrations measured in Delray Beach were similar in May and January and were lo wer than in Belle Glade. This study suggests that the pre-harvest burning of sugarcane could significantly impact the regional air quality of PBC and surrounding areas. Research Objective Previous studies dem onstrate that s ugarcane burning could be a significant contributor to local atmospher ic pollution; however, the cu rrent EFs for sugarcane preharvest burning are limited and unreliable. Further research is warranted in order to better assess the impact of the emissions from this source. The objective of this study was to develop EFs for specific hazardous ai r pollutants (PAHs, carbonyls and VOCs) and PM2.5 from sugarcane burning using a com bustion chamber that simulates field burning. In addition to measuring the mass based PM2.5 EF, the composition of PM was

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25 analyzed by measuring the EC and OC fractions. CO and CO2 concentrations were also measured to evaluate the combustion efficiency. Table 1-1. Published AP-42 EFs for sugar cane pre-harvest burning (USEPA, 1995) Particles (kg/Mg) CO (kg/Mg) Methane (kg/Mg) Nonmethane organic compounds (kg/Mg) Sugarcane 2.3-3.5 30-41 0.6-2 2-6 A B Figure 1-1. Florida sugarcane field burning. A) initiation of plot burning by lighting the perimeter of the field. B) picture of smoke plume produced during burning

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26 CHAPTER 2 EXPERIMENTAL METHODOLOGY Summary of Experimental Approach Sugarcane biomass was collected from a variety of sources over the course of the study. Both dead (dry) leaves and whole stalks (containing green and dry leaves) were collected for different experiments. Sugarcane wa s collected from South Florida fields in March 2008, December 2008, and May 2009. Sugarcane was als o collected from University of Florida plots in Gainesville, FL (September 2009) and Citra, FL (November 2009 and January 2010). No effort was made to collect sugarcane from a consistent plot of land, but after collection the bi omass was handled the same (stored in an outdoor shed in plastic bags). No obvious changes in the dry leaves were observed from the time of collection to burning; however, whole sugarcane stalks gradually dried out during the storage time. A combustion chamber was built to simulate field burning. Sugarcane was fed into the chamber in a way to create near cons tant burning conditions. Various pollutants were sampled from the c hamber following EPA methods and analyzed to quantify the EFs. Combustion Chamber Design An open burning combustion chamber, shown in Figur e 2-1, was built to simulate field burning. The combustion chamber cons isted of three sectionsthe combustion section, a cone, and a sample transport duc t. The combustion chamber was open to the atmosphere on the bottom to ensure adequate air was available for combustion reactions. The entire chamber and stack was lined with aluminum foil to prevent the

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27 catalytic formation of PAHs, which is associated with steel materials (Jenkins et al., 1996b). The cone served to direct exhaust gas from the combustion chamber to the stack. To mix the combustion gases before samp ling, 2 baffles (made of aluminum) were placed in the stack. Each baffle covered appr oximately half of the stack area. A draft inducer (Auto-Draft Inucer M odel I, Tjernlund Products, Inc.) was employed near the exit of the stack to stabilize the pressure as well as induce excess air into the chamber. Experimental Procedures For most experiments, only dry leaf tr ash was burned. A few experiments burned entire sugarcane stalks, whic h included the sugarcane stalk, some wet (i.e., green) leaves, and dry leaves. The purpose of the later experiments was to observe the effect of MC and biomass composition on the EFs To facilitate the burning process, leaves were pre-weighed in batches of approximately 100 g. A butane lighter (BIC) was used to init ially light the biomass, after which the sampling was start ed. Leaves were fed into the chamber at a rate of approximately 100 g every 40 seconds, in or der to create near constant burning conditions. The flame was sustained through t he constant feeding of biomass during the experiment. Sampling was stopped immediatel y after the flame was visually observed to cease. In whole stalk experiments, cons tant burning conditions were attempted, but the combustion was much harder to contro l due to the more heterogeneous nature of the biomass. After experiment s finished, any material (sta lks) that did not burn was weighed to determine the net amount of biomass combusted. In dry leaf experiments, post weighing was not performed because t he remaining ash was minimal. The sampling and analytical methods were based on EPA promulgated test methods. Some

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28 test methods were adapted for stack samp ling applications. Stack sampling meter boxes (containing a pump, dry gas meter (D GM), inclined manometer, and temperature sensors) were used to control the sampling flow rate and record the volume of gas sampled. The meter boxes and dry gas meters were calibrated using a certified dry gas meter once. Sampling was conducted from a roof posit ioned near the sampling point; therefore, sampling lines were kept less than 12 inches, minimizing losses in the sampling lines. Additionally, all sample lines were heated to prevent condensation within the sampling lines. Only one pollutant was sampled per expe riment. The sampling time and flow rates varied between each method and are discussed in more detail in the following sections. The sampling point was approxim ately 8 duct diameter s downstream of the baffles, to be consistent with EPA stack sampling protocols (USEPA, 2000a). Due to the short duration of experiments and limitations in space, the sampling probe was kept at the same point throughout the experiment. To test whether sampling at a single point was representative of the entire stack cross-secti on, a gas uniformity test was conducted. For each sample, a field data sheet was completed including the following information: experiment date, time, name; ambient temperature and pressure; sampling rate; mass of leaves burned; DGM start and finish volume s; DGM inlet and outlet temperatures; DGM pressure; and any comments about the experiment. Prior to the start of experiments, leak checks were perfo rmed by closing off the sampling inlet and observing movement on the DGM dial. If a leak was detected, the sampling line was

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29 inspected and leaks were repaired. If the l eak could not be repaired, the leak rate was recorded and the sample volume was corrected. PAH, carbonyl, and VOC sample extraction and analysis was performed by Columbia Analytical Services (CAS), which is certified by the Florida Department of Health (NELAP Certification E871020). A formal Quality Assurance Project Plan (QAPP) was prepared and approved by the EPA to ensure meaningful data was obt ained. When procedures were changed, the QAPP was updated and submitted for review and approval. Quality assurance (QA) and quality control (QC) meas ures are described in the following sections. Uniformity Test Since sam ples were collected from one point in the stack, it is important to evaluate whether the ex haust gases were uniformly mixed at the point of sampling. To accomplish this, oxygen concentrations were measured with a real-t ime oxygen monitor (Rapidox 3000) at five random points in t he stack cross-section. 100 g of sugarcane was burned, and the oxygen co ncentrations were measured every second during the burning cycle, which lasted approximately 2 minutes. A one-way ANOVA statistical test was performed to identify any significant concentration differences between various points in the duct cross-section. Polycyclic Aromatic Hydrocarbons PAH sampling and analysis was based on EPA method TO-13A (U SEPA, 1999a), modified for stack sampling. The PAH co mpounds investigated in clude: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k]fluoranthene,

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30 benzo[ a ]pyrene, indeno[1,2,3cd ]pyrene, dibenz[ a,h ]anthracene, and benzo[ g,h,i ]perylene. The PAH compound structures are displayed in Figure 2-2. Sampling The PAH s ampling train is shown in Fi gure 2-3. PAH sampling was performed by passing sample gas through a quar tz filter (to collect parti culate PAHs) and a sorbent cartridge containing polyurethane foam (PUF) and XAD-2 resin (to collect semi-volatile PAH compounds). All samples lines were co mposed of stainless steel and heated with heating tape during sampling. Because PAH compounds exist partially in the particulate phase, sampling was performed isok inetically. The sampling flowrate was manipulated in order to match the sampling velocity through the nozzle to the measured stack velocity. Prior to sampling, the quartz filters were baked at 400 C for 5 hours and stored in a dessicator until use. Sorbent cartridges were prepared, cleaned, and certified clean by CAS. In between experiments, samples lines were rinsed with hexane and air-dried. Following sampling, filters and sorbent cartridges were immediately wrapped in hexane rinsed aluminum foil and stored below 4 C until shipment. Samples were usually shipped the next day, except in t he cases where experiments were conducted on Friday or Saturday. Samples were shipped in dry ice for preservation and were extracted within 7 days of collection. Analysis CAS performed all sample extraction and analysis procedures in accordanc e with EPA Method TO-13A. Briefly, filters and cart ridges were Soxhlet extracted together in a mixture of 10% diethyl ether in hexane for 18 hours and the extract was concentrated

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31 using a turbo-vap evaporator (Zymark). The extract was then injected into a gas chromatograph (GC) (Hewlett Packard 58900II+) with a fused silica capillary column to separate the analytes and a mass spectromet er (MS) (Hewlett Packard 5972A) was used in the full range data acquisition (SCAN) mode to detect the analytes. Compounds were identified by comparing the mass spectr a of the samples to those of reference materials. The compound concentrations we re quantified using an internal standard calibration, whereby the analytes responses were compared to the responses of internal standards that were added to the sample prior to the analysis. QA/QC A number of QA/QC measures and samples were taken in order to ensure the integrity of the PAH data: One field blank was collected to detect any contamination introduced through handling or storage procedures. The field blank was treated the same as test samples; however, no sample air wa s drawn through the cartridge. Ambient blank samples were collected at the beginning of each experiment day to measure the background concentrations of t he compounds of interest in the area. Two samples, collected in parallel, were used to measure the precision of the sampling and analysis. Parallel samples we re collected in 40% of experiments. A laboratory method blank was run with eac h batch of samples analyzed to ensure there was no contamination in the laboratory methods or in the cartridge itself. The laboratory method blank was a clean sorbent cartridge and filter that was treated the same as a sample. All analyt ical steps were conducted the same as sample analysisusing all reagents, standards, surrogate compounds and glassware that were used fo r the sample analysis. Laboratory control sample (LCS) and a duplicate laboratory control sample (DLCS) were run with each batch of sa mples analyzed. LCSs and DLCSs served to monitor the extraction efficiency of target analytes from clean sorbent cartridges. Clean sorbent cart ridges were spiked with known concentrations of the target analytes and processed with the same extraction and analysis procedures as the field samples. LCSs and DLCSs were run with every group of samples analyzed.

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32 Surrogate compounds (fluorene-d10 and pyr ene-d10), which are similar to the target compounds but are not naturally found in environmental samples were spiked onto the method blank, lab control sample, duplicate lab control sample, and each sample analyzed to evaluate and monitor for unusual matrix effects, sample preparation errors, and analysis errors. Carbonyls Carbonyl s ampling and analysis follow ed a modified EPA Method TO-11A (USEPA, 1999b), adapted for stack sampling. Carbonyl compounds that were investigated include: formaldehyde, ac etaldehyde, propionaldehyde, crotonaldehyde (total), butyraldehyde, benzal dehyde, isovaleraldehyde, valeraldehyde, o-tolualdehyde, m,p-tolualdehyde, n-hexaldehyde and 2,5-dimethylbenzaldehyde. Sampling The carbonyl sampling train is shown in Figur e 2-4. Commercially available cartridges pre-coated with 2, 4-dinitrophenylhydrazine (DNPH) (Supleco) were used to sample carbonyls. A LpDNPH (Supleco) ozone scrubber was placed before the DNPH cartridge to remove ozone interferences. The sampling line was made of stainless steel and brass and was heated with heating tape. Between experiments the sample line was purged with pure nitrogen gas. Following sampling, cartridges were stored in a freezer until shipping. Cartridges were sent to CAS (with dry ice for pres ervation) and were analyzed within 5 days of collection. Analysis CAS performed all sample extraction and anal ytical procedures in accordance with Method TO-11A. The sample cartridges were eluted wit h acetonitrile and analyzed by isocratic reverse phase high performance li quid chromatography (HPLC) (Waters LC

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33 Module I Plus or Hewlett Packard HP 1050) with an ultraviolet absorption detector operated at 360 nm. QA/QC A number of QA/QC measures and samples were taken in order to ensure the integrity of the carbonyl data: One field blank was collected to detect any contamination introduced through handling or storage procedures for each lot of DNPH cartridges used. The field blank was treated the same as test samp les; however, no sample air was drawn through the cartridge. Ambient blank samples were collected at the beginning of each experiment day to measure the background concentrations of t he compounds of interest in the area. A breakthrough test was conducted by plac ing two DNPH cartridges in series. The backup cartridge was analyzed to ensure no compounds were detected (i.e., no breakthrough occurred during sampling). Parallel samples were collected in 4 out of 5 experiments to determine the precision. A blank cartridge was analyzed with each batch of samples to detect contamination from t he sample cartridges or analytical methods. Volatile Organic Compounds EPA Metho d 18 was applied for the samp ling of VOCs (USEP A, 2000b) and EPA Method-TO-15 (USEPA, 1999c) was applied for the analysis (performed by CAS). Benzene, toluene, o,m,p -xylenes, ethylbenzene and styrene compounds were investigated. Sampling Method 18 involv es collecting gas samples in Tedlar bags using a Vac-U-Chamber (SKC). The Vac-U-Chamber is a rigid air sa mple box that allows for bags to be filled directly by using negative pressure. T he sample bag (contained in the Vac-U-Chamber) was connected to the sample probe with Tefl on tubing. The air-tight chamber was

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34 evacuated with a vacuum pump causing the T edlar bag to fill with sample gas. Figure 25 shows a picture of the Tedlar bag contai ned within the Vau-U-C hamber prior to the start of an experiment Prior to use, Tedlar bags were purged 5 ti mes with pure nitrogen gas. Tedlar bags were never reused. After samples were coll ected they were protected from UV light until analysis. The time between sample collection and analysis was minimized as much as possible and never exceeded 72 hours. Analysis CAS performed the analysis in ac cordance with Method TO-15. The analysis procedure involves pre-concentrating a know n volume of air on a solid adsorbent trap and then analyzing with GC/MS (A gilent 6890N/5975). Analyt es were identified by comparing the mass spectra of the samples to those of reference materials. The compound concentrations were quantified using an internal standard calibration, whereby the analytes responses were compared to the responses of internal standards that were added to the samp le prior to the analysis. QA/QC A number of QA/QC measures and samples were taken in order to ensure the integrity of the data: Ambient blank samples were collected at the beginning of each experiment day to measure the background concentrations of t he compounds of interest in the area. Parallel samples were collected in 100% of the VOC experim ents performed. Method blanks were performed to detect contamination in the analytical procedures. With each batch of samples analyzed, a LCS was prepared by spiking a Tedlar bag with known concentrations of the ta rget analytes. The bag was analyzed to evaluate the analytical methods recovery.

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35 Surrogate compounds (1,2-dichloroethande -d4 and toluene-d8) were spiked into each sample analyzed to measure their recovery. To determine EPA Method 18s ability to accurately measure all compound concentrations, a canister with spiked compounds in known concentrations was sampled exactly how experiments were conducted. The bag sample was then analyzed, and the recovery of each compound was determined. PM2.5 PM2.5 sampling was based on EPAs Other Test Methods (OTMs) 27 and 28 (USEPA, 2008a; USEPA, 2008b) to measure t he filterable and condens able PM (CPM), respectively. Filterable PM is defined as any PM that can be collected on the filter at the sampling point temperature. CPM is any PM that may form or condense as the exhaust gases are cooled to below 85 F. Since the stack gas temperature in our experiment exceeded 85 F, an impinger train (based on OTM 28) was used to cool the exhaust gases and collect the CPM in some experiment s. In addition to determining the PM2.5 mass EF, PM samples were also collected on tissuquartz filters to determine the mass emission rates of EC and OC. Sampling Figure 2-6 displays the sampling train, whic h was modified slightly from Methods 27 and 28. Exhaust gas was sampled isok inet ically, passed through an in-stack, size selective cyclone (Sierra Instruments, Inc. Series 280 CycladeTM) to remove particles larger than 2.5 m and then passed through a glass fi ber filter (Type A/E, Gelman Sciences, Inc.) to collect t he filterable particulate matter. In some experiments, an impinger train was added to collect and analyze CP M. The impinger train serves to cool the gas to <85 F. A temperature sensor was used in the impinger train to ensure the temperature was less than 85 F at the CPM filter. CPM was collected in the impinger

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36 train and on a Teflon filter (Zefluor, Pall Li fe Sciences). PM samples for the EC/OC analysis were collected the same as filter able PM samples except a tissuquartz filter (Catalog number 2500QAT-UP, Pall Life Sciences) was used in place of the glass fiber filter. The actual cut size of the cyclone is dependent on the gas viscosity, which is a function of temperature. Since the average temperature fo r each experiment varied, the actual cyclone cut-points varied slightly, but can be calculated using Equation 2-1, which was determined in the cyclone calibr ation performed by the manufacturer. 80.0 5009.3024.0 Q D (2-1) where D50 is the cyclone cut-point (m), Q is the sampling flow ra te (acfm) at the inlet of the cyclone at actual stack temperature and pressure, and is the gas viscosity (micropoise) that is calculat ed using Equation 2-2 T 406.04.174 (2-2) where T is the stack gas temperature in C. Glass fiber and Teflon filters were baked for at least 3 hours at 105 C prior to use. Tissuquartz filters used for EC/OC analysis were baked at 550 C for 12 hours and allowed to cool for 12 hours to remove any residual carbon in t he filters. All filters were wrapped in aluminum foil and stored in a dessicator chamber until use. Analysis Following sampling, the glass fiber filters were placed in a Petri dish and into a dessicator chamber to equilibrate at lo w humidity for at l east 24 hours before determining the post weight. The front half of the filter holder and cyclone exit were rinsed with acetone, transferred to a pre-we ighed weighing dish, and also weighed as

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37 part of the filterable PM mass. A microbalance (Model MC 210 S, Sartorius Corp.; readability 10 g) was used for all weighing. Filter and dishes were weighed 3 times to determine the average mass and were repeatedl y weighed at intervals of at least 6 hours to ensure the weight was constant (defined as having a weight change of less than 0.5 mg over at least a 6 hour period). For the CPM recovery, the impingers were rinsed three times with ultra-high purity deionized (DI) water to collect inorganic so luble PM. Following the water rinses, the impingers were rinsed once with acetone and t wice with methylene chloride to collect the organic fraction of the PM The inorganic (i.e., water) and organic (i.e., acetone and methylene chloride) rinses were kept separat ely. The CPM filter was extracted in an ultrasonic bath three times with DI water and three times with me thylene chloride and the extracts were added to the inorganic and or ganic rinses, respectively. In accordance with Method 28, the water rinses were extrac ted with methylene chloride in a separatory funnel to remove any organic PM that ma y have been included with the initial water rinses. The inorganic fraction was taken to dr yness, 100 mL of DI water was added to re-dissolve the residual, and the mixture was ti trated to a pH of 7.0 using 0.1 N ammonium hydroxide to neutralize acids and re move waters of hydration. Then both the inorganic and organic rinses were allowed to evaporate to dryness and the remaining residue was weighed to det ermine the condensable PM mass. The glassware used in the sampling train and analytical procedures was meticulously cleaned before use. Glassw are was soaked in a soapy water bath, cleaned in an ultrasonic bath with DI water for at least two, sixty minute cycles, and rinsed with acetone and two rinses of methylene chloride. Finally, the glassware was

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38 baked at 300 C for 6 hours. During storage and transportation to and from the field, all glassware openings were cover ed using aluminum foil. Tissuquartz filters were sent cold to the Research Center for Environmental Changes, Academia Sinica in Taipei, Taiwan, where they were analyzed for EC and OC using a semi-continuous OCEC Carbon Aerosol Analyzer (Sunset Laboratory, Model 4) following the National Instit ute for Occupational Safety and Health (NIOSH) method 5040 (NIOSH, 1999). In the analysis, a portion of t he filter is heated at distinct intervals to 600 C in a pure helium atmosphere to volatilize the organic carbon. The sample is then cooled and re-heated at intervals in a 2% oxygen in helium atmosphere to evolve the elemental carbon. The evolve d fractions are oxidized to CO2 and reduced to CH4 and analyzed by a flame ionization detector (FID). QA/QC A number of QA/QC measures and samples were taken in order to ensure the integrity of t he PM data: Ambient blanks were collected in the fiel d at the beginning of each experiment day for filterable particulate matter and EC /OC filter samples. Because the temperature was always below 85F in the field for ambient samples, the impinger train was not used as part of these blank experiments. Lab blanks were run using the entire CP M impinger train setup and reagents used for analysis. The lab blank served to measure the contamination introduced into the analysis from the rinsin g reagents and sealant used to lubricate the impinger connections. Filter laboratory blanks were used in the EC/OC analysis. The laboratory filter blank served to detect any background carbon concentrations within the clean filter. Flue Gases To evaluat e the combustion conditions of our experimental system, CO, CO2 and O2 concentrations were measured in a few experiments. Gas monitors were rented for

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39 one 1 month; therefore, flue gases were not monitored during every sampling campaign. However, since burning procedure s were consistent across all experiments the combustion efficiency is expected to be similar. Table 2-1 summarizes the instruments used for the gas monitoring. Gases were sampled from one sample probe in the stack and passed through a gas conditioner (Universal Dual Pass) to cool and dry the exhaust gases before di recting them to the gas analyzers. Data was recorded on a 1 second, real-time basis and recorded on a datalogger (Monarch 2000). CE is defined as the fraction of carbon released as CO2. In this study, the modified combustion efficiency (MCE) was determined using Equation 2-3, which assumes all of the carbon is released as CO or CO2. MCE CO2 CO2 CO (2-3) [CO] and [CO2] are the mass concentrations of CO and CO2 in excess of the background. Previous studies have demonstrat ed that over 95% of carbon is released as CO or CO2; therefore, it is accurate to estimate the CE without measuring hydrocarbons or particulate matter (Ward and Hardy, 1991; Gupta et al., 2001; Chen et al, 2007). Instruments were calibrated before eac h experiment using EPA protocol gases. The CO analyzer was zeroed with zero air and calibrated at 2173 ppm. The CO2 monitor was zeroed with high purit y nitrogen and calibr ated at 6% CO2. The oxygen monitor was zeroed with pure nitrogen and ca librated with ambient air (20.9% O2). Span checks were performed on the CO and CO2 monitors using 1088 ppm CO and 3% CO2

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40 gas. Span checks served to ensure the lineari ty of the instrument response and calibration. Temperature and Pressure In order to calculate the velocity in t he stack and the chamber volumetric flowrate, the pressure and temperature were monito red in the stack in accordance with EPA Method 2 (USEPA, 2000c). The pressure was measured using a s-type pitot tube connected to an inclined manometer and the temperature was measured wit h a thermocouple. Pressure and temperature we re monitored throughout the experiment at centroid points along a horizontal traverse of the stack at the same level as the sampling point. Figure 2-7 shows the pressu re and temperature me asurement points. For longer sampling periods, the pitot tube and thermocouple were moved along the traverse to each measurement point; how ever, for shorter sampling periods they were kept stationary at one point. The pre ssure and temperature were recorded at regular intervals (about ever y 30 sec.). Using the aver age temperature and pressure measured, the average stack velo city was calculated using Equation 2-4. vs KpCp Pavg Ts ( avg )PsMs (2-4) where vs is the average stack gas velocity (ft/s), Kp is a constant equal to 85.48 ft/s (lb/ lb. mole R)1/2, Cp is the pitot tube coefficient (0.84), Ts(avg) is the average stack temperature (R), Ps is the absolute stack gas pressure (in. Hg) (assumed to be atmospheric pressure since the sampling poin t was near the exit of the stack, which was at atmospheric pressure), and Ms is the molecular weig ht of the stack gas (calculated from flue gas data to be 29.2 g/mole).

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41 The standard volumetric flowrate was calculated using Equa tion 2-5. Q 60(1 Bws) vxA TstdPsTsPstd (2-5) where Q is the volumetric flow rate (scfm), Bwo is the proportion of volume of water vapor in the gas stream, A is the cross-sectional area of the stack (ft2), Tstd is the standard condition temper ature (530 R), and Pstd is the standard pressure (29.92 in. Hg). The Bwo of the gas stream was calculated by measuring the weight change of an impinger filled with silica gel submerged in an ice bucket (to condense the water). Since Bwo was found to be less than 0.01, it was negl ected when calculating the volumetric flowrate. EF Calculation EFs were calculated using Equation 2-6 (Dhammapala et al., 2006), which assumes the chamber to be well mixed. EF C x Qchamber t mburned (2-6) where Cx is the measured pollutant concentration minus the ambient concentration, Qchamber is the flowrate through the cham ber, t is the sampling time, and mburned is the mass of biomass burned. In the case w here ambient concentrations were below detection limits, the background concentrati on was assumed to be zero for the EF calculations. All sample volumes and chamber flowrates were corrected to standard conditions (530 R and 29.92 in. Hg). Table 2-1. Gas analyzer summary Gas Analyzer model (manufacturer) O2 Rapidox 3000 (C abridge Sensotec) CO 48C (Thermo Electron Corporation) CO2 1400 (Servomex)

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42 Figure 2-1. Combustion chamber

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43 Naphthalene Acenaphthylene Acenaphthene Benz[ a ]anthracene Benzo[ b ]fluoranthene Anthracene Benzo[ k ]fluoranthene Benzo[ g,h,i ]perylene Benzo[ a ]pyrene Chrysene Fluoranthene Fluorene Phenanthrene Pyrene Indeno[1,2,3c,d ]pyrene Figure 2-2. PAH compound structures

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44 Figure 2-3. PAH sampling train Figure 2-4. Carbonyl sampling train

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45 Figure 2-5. Tedlar bag cont ained in Vac-U-Chamber Figure 2-6. PM2.5 sampling train

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46 Figure 2-7. Pressure and tem perature measurement points

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47 CHAPTER 3 RESULTS Uniformity Test Figure 3-1 shows the O2 gas concentrations at each measurement point over the duration of the test. To identify any signifi cant concentration differences between the measurement points, a one-way ANOVA statistical analysi s test was performed. A p value of 0.33 was obtained, si gnifying there were no signif icant differences among the measurement points (i.e., t he combustion gases are uniformly mixed). Therefore, sampling at one point in the stack cro ss section provided a representative measurement. Flue Gases Flue gases were recorded during 3 major burning events for dry leaves. Figure 32 shows an example plot of the flue gas concentrations and MCE for a burn of 2 kg of dry leaves. The leaves were added at a ra te of 100 g about every 40 seconds. The peaks and valleys in the flue gas concentrations correspond to the changing intensity of the fire as a result of t he feeding process. The dashed li ne marks the time when the flame was visually observed to cease (at whic h pollutant sampling was stopped). At this point the MCE drops due to the high CO relative to CO2 concentrations associated with the smoldering phase of combustion. Based on the three experiment s, the average MCE was 98.5 0.21 for the flaming phase of combustion. The high combustion efficiencies exhibited in this experiment indicate PAHs the dominance of flami ng combustion in this studied scenario.

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48 PAHs Five PAH experiments were conducted, totaling 7 samples (two experiments collected parallel samples). Tests 1-3 used solely dry leaves, whereas Tests 4 and 5 used whole sugarcane stalks with a mixt ure of dry and green leav es. Table 3-1 summarizes the sampling conditions for each experiment. Samples were named for their sample type (i.e. ambien t, field blank or test), t he number denotes the experiment number, and the letter (i.e. a and b) denotes par allel samples. Sampling conditions are not applicable (NA) for the field blank, since no sample was taken for this test. Due to the complex nature of the extraction and analytic al procedures in Method TO-13A, some analytical bias is expected. Hence, extensive QC samples (surrogate spikes, LCS, and DLCSs) are used to monitor for these effects. To account for the differences in extraction and recovery e fficiencies between experiments, concentrations were adjusted based on the compound recoveries in the LCS and DLCS samples as well as the surrogate compound recoveries. Equation 3-1 shows how the adjusted (true) concentration was calculated. Concentrationtrue Concentrationmeasured,sample % recover y surrogate,LCS&DLCS% recoverycompound,LCS&DLCS %recoverysurrogates,sample (3-1) where Concentrationmeasured,sample is the measured concentration in the sample, %recoverysurrogates,LCS&DLCS is the average % recovery of the surrogate compounds in the LCS and DLCS, %recoverycompound,LCS&DLCS is the average % recovery of the specific PAH compound in the LCS and DLCS, and %recoverysurrogates,sample is the average % recovery of the surrogate compounds in t he sample. Each experiment and the results are explained in detail in the following sections.

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49 Test 1 (5/14/09) Table 3-2 summarizes the sample concent rations, minimum reporting limit (MRL), and EFs for Test 1. The total EF for th is experiment was 5. 92 mg/kgdominated by naphthalene, which contributed to 68% of PAH emissions. The other major compounds were acenaphthylene and phenanthrene, wh ich contributed to 11% and 10%, respectively, to the total PAH EF. Heav ier molecular weight compounds were not detected (ND) in this test. Table 3-3 su mmarizes the QA/QC results for the LCS and DLCSs as well as surrogate compound reco veries. The sample concentratio ns and EFs presented in Table 3-2 have already be en corrected to account for the recovery efficiencies. Test 2 (5/27/09) Two samples were collected in pa rallel in Test 2. Table 3-4 summarizes the results of Test 2 and Table 3-5 summarizes the QA/QC results. The total PAH EF was 7.21 0.27 mg/kg. Again, the most abundant compound was naphthalene comprising 66% of PAH emissions followed by acenaphthylene and phenanthrene. Fluorene, anthracene, fluoranthene and pyrene composed a much sm aller portion of the PAH emissions. Tests 3-4 (6/12/09) Table 3-6 and Table 37 summarize the results for Test 3 and Test 4 and the QA/QC results, respectively. The total PAH EF was 8.16 mg/kg for test 3. 70% of emissions are attributed to naphthal ene. Acenaphthylene and phenanthrene each contributed to 10% of emissions, respecti vely. Test 4, which used whole sugarcane stalks, exhibited the highes t PAH EF.91 mg/kg. Emissions were dominated by naphthalene, acenaphthylene an d phenanthrene, similar to all other experiments.

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50 Test 5 (1/27/10) Two parallel samples were collec ted in Test 5, which bur ned whole sugarcane stalks. Table 3-8 summarizes the PAH co ncentrations and EFs determined for this experiment. Table 3-9 displays the QA/QC results. The total PAH EF was 6.32 0.65 mg/kg, which is similar to t he dry leaf experim ents and significantly lower than the other whole leaf experiment (Tes t 4). Although Test 5 exhi bited the highest pollutant concentrations of all experiments, the EFs were lower due to the shorter experimental time (indicating denser fuel loading and qui cker combustion conditions). Numerous heavier molecular weight compounds, which were not detected in previous experiments, were quantifiable in this test. Compared to the previous experiments, naphthalene contributed less to the total PAH EF (ave rage 59%) and the contribution from heavier molecular weight compounds, such as fluor anthene and pyrene, was increased. Carbonyls Five carbonyl experim ents were conducted. Three experiments (Tests 1-3) used solely dry leaves and two experiments (Tests 4,5) used whole sugarcane stalks. Table 3-10 summarizes the sampling conditions fo r each experiment. Sa mple flow rates ranged from 0.027-0.062 ft3/min and the sampling time r anged from 3 to 20 minutes. Most experiments burned 1 kg of dry leaves ex cept test 5, which burned approximately 253 g. Test 1 (3/31/09) In Test 1 a field blank, ambient blank, test sample, and breakthrough sample were collected. Table 3-11 summarizes the measur ed concentrations, MRLs and EFs for test 1. All compounds of interest were below detec tion limits in the field blank, ambient blank and breakthrough samples. The total carbony l EF was 178.3 mg/kg and formaldehyde

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51 was the most dominant carbonyl compound a ccounting for 64% of measured carbonyl emissions. Other compounds detected in cluded acetaldehyde, propionaldehyde and valeraldehyde. Since this experiment reveal ed that no sampling breakthrough occurred, backup cartridges were not used in subsequent experiments. Tests 2-4 (5/28/09) Three experiments were conducted on 5/28/ 09. Tests 2 and 3 used dry leaves, whereas T est 4 used whole s ugarcane stalks. Test 3-12 summarizes the concentrations and EFs for these experiments. The EFs were 186 58.0 mg/kg and 228 7.78 mg/kg for tests 2 and 3, respectively. Test 4 (with whole stalks) exhibited a much higher total EF: 482 15.9 mg/kg. Again formaldehyde was the most abundant compound followed by acetaldehyde. Test 5 (12/13/09) In Test 5, whole sugarcane stalks were burned; howev er, it should be noted that the sugarcane stalks were from a different source than the pr eviously tested stalks (on 5/28/09). Table 3-13 displays the results. Test 5 exhibited the highest EFs of all experiments: 1401.3 166.2 mg/kg. Except for butyraldehyde, all previously detected compounds were present in this test. Cr otonaldehyde was also detected, which was below detection limits in previous experiments. VOCs A total of 4 VOC experiments were conduc ted (using dry leaves) during two testing campaigns on 6/1/09 and 9/29/09. Two samples were collected in parallel for each experiment, resulting in 8 to tal samples. Table 3-14 summari zes the test con ditions for each experiment. All experiments burned 300 g of biomass and the sampling time was

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52 around 3 minutes. The results of each ex periment are described in the following sections. Tests 1 & 2 (6/1/09) Table 3-15 summarizes the measured conc entrations and EFs for the samples. The total VOC EF was 26 2.0 mg/kg and 22.6 2.5 mg/kg for Tests 1 and 2, respectively. In all experiments, benz ene was the most domi nate compound with EFs ranging from 16-18.7 mg/kg followed by tolu ene with EFs ranging from 3.6-5.2 mg/kg. m,p -xylenes and ethylbenzene follo wed in abundance and styrene and o -xylene had the lowest EFs. All compounds were below the detection limit in the method blank sample. The surrogate compound recovery was excellent ranging from 97-111% and 95-103% for 1,2-dichloroethane-d4 and toluen e-d8, respectively. The reco very efficiencies for the LCS also met acceptance limits and are presented in Table 3-16. Tests 3 & 4 (9/29/09) Table 3-17 summarizes the results for V OC Tests 3 and 4. Except for toluene, all compounds in the ambient sample were below the detection limits. The total VOC EF was 25.23.5 mg/kg and 22.01.0 mg/kg for tests 3 and 4, respectively. As in Tests 1 and 2, benzene was the most dominate compound followed by toluene, m,p -xylenes, ethylbenzene, o -xylene and styrene, in descending order. All compounds were below the detection limits in the method blank sample. The spike recovery efficiencies met all acceptanc e limits with recovery efficiencies ranging from 94-102% for 1,2-dichloroethande-d4 an d 101-103% for toluene-d8. The LCS was

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53 also within the recovery efficiency acceptance limits. The LCS data is summarized in Table 3-18. Recovery Study A sample was collected on 11/23/09 from a spiked canister containing sample gas with the target compounds in known concent rations. The sample was analyzed on 11/24/09, to be consistent wit h the average sample storage time of our experiments. The spiked concentration, measured concentr ation, and % recovery are shown in Table 3-19. As can be seen from this test, the recove ry of the target com pounds is rather low, especially for heavier molecular weight com pounds like styrene, which had a recovery efficiency of only 51%. The results of this recovery study imply that EPA method 18 may not be an accurate method for the compounds of interest in this study, even when proper protocols are followed, because of signi ficant sample losses during storage and transport. Compounds may be lo st to the bag surface or undergo chemical reactions and transformation from the time of collection to analysis. It should be noted that the VOC EFs presented in this study probably underestimate the true EFs. PM2.5 Mass EFs Five PM sampling experiments were conduc ted. Three experiments (Tests 1-3) sampled filterable and condensable PM together. Tests 4 and 5 sampled only the filterable PM (without the impinger trai n). Table 3-20 summarizes the sampling conditions for all ambient and test PM experiments.

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54 Table 3-21 displays the analytical results for all PM experiments. Note that laboratory blank samples were collected in dependently of ambient blank samples. Filterable PM EFs were not determined for the 10/3/09 (acetone rinses could not be quantified) and 10/10/09 experim ents (filter was too damaged to post weigh). However, the October 2009 experiments and 1/14/10 experiment were used to evaluate the contribution of CPM to the to tal PM mass. A t-test was per formed to compare the blank and test samples with respect to the condensable PM mass. The results show that the condensable PM mass is not statistically hi gher in the test samples compared to the blank measurements (p value=0.2673). Ther efore, it was concluded that the CPM fraction would not significantly contribute to the PM EF an d was thus excluded from the PM EF calculation. Ambient blank PM conc entrations were subtracted from sample PM concentrations when calculating the EFs. PM EFs ranged from 1.6 g/kg to 3.17 g/kg. EC and OC EFs Three samples were collected for EC and OC analys is. In addition, a laboratory blank and one ambient sample (per exper iment day) were analyzed. Table 3-22 summarizes the experimental conditions. Table 3-23 summarizes the analytical result s and EFs. OC adsorption on to filters, resulting in a positive artifact, is a doc umented occurrence (Dhammapala et al., 2007a), which was observed in this experiment by the presence of OC in the laboratory blank and ambient blank samples. To correct for this artifact, am bient OC concentrations were subtracted from the measured OC concentration when determi ning the OC EF. OC EFs ranged from 0.15-0.35 g/kg and were lowe r than EC EFs (range: 0.71-0.93 g/kg).

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55 Table 3-1. PAH experiment sampling conditions Date Sample ID Percent isokinetic Time (min) Sample volume (ft3) Average stack temp. (F) Qchamber (ft3/min) mburned (kg) Ambient-1 10130.0014.574 225 0.0 5/14/09 Test-1 9429.459.4388 183 3.6 Ambient-1 8230.0012.475 237 0.0 Test-2a 8837.5811.4392 162 4.0 5/27/09 Test-2b 8837.589.7392 162 4.0 Ambient-3/4 9140.0517.486 225 0.0 Test-3 8858.7711.1353 188 6.0 6/12/09 Test-4 9768.1513.6400 186 8.9 Ambient-5 9732.0018.569 152 0.0 Field Blank-5 NA NA 0.0NA NA NA Test-5a 10228.5711.3466 131 8.6 1/29/10 Test-5b 10228.5711.9466 131 8.6 Table 3-2. Test 1 PAH concentrations and EFs Sample ID Compound Concentration (g/ft3)MRL (g/ft3) EF (mg/kg) Naphthalene ND 0.340 NA Ambient-1 All (excluding naphthalene) ND 0.034 NA Naphthalene 2.72 0.540 4.05 Acenaphthylene 0.44 0.054 0.66 Fluorene 0.13 0.054 0.20 Phenanthrene 0.39 0.054 0.58 Anthracene 0.07 0.054 0.10 Fluoranthene 0.12 0.054 0.18 Test-1 Pyrene 0.11 0.054 0.16

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56 Table 3-3. Test 1 QA/QC results % Recovery Compound LCS DLCS Test-1 Naphthalene 81 83 NA Acenaphthylene 80 84 NA Acenaphthene 85 91 NA Fluorene 92100 NA Phenanthrene 93 97 NA Anthracene 90 94 NA Fluoranthene 107107 NA Pyrene 107107 NA Benz[ a ]anthracene 105103 NA Chrysene 98 99 NA Benzo[b]fluoranthene 114115 NA Benzo[ k]fluoranthene 105114 NA Benzo[ a ]pyrene 105104 NA Indeno[1,2,3cd ]pyrene 114115 NA Dibenz[ a,h ]anthracene 116116 NA Benzo[ g,h,i ]perylene 121121 NA Fluorene-d10 100102 100 Pyrene-d10 115115 116 Table 3-4. Test 2 PAH concentrations and EFs Sample ID Compound Concentration (g/ft3)MRL (g/ft3) EF (mg/kg) Naphthalene ND 0.400 NA Ambient-2 All (excluding naphthalene) ND 0.040 NA Naphthalene 3.00 0.450 4.56 Acenaphthylene 0.54 0.045 0.82 Fluorene 0.18 0.045 0.27 Phenanthrene 0.52 0.045 0.80 Anthracene 0.11 0.045 0.17 Fluoranthene 0.14 0.045 0.21 Test-2a Pyrene 0.12 0.045 0.19 Naphthalene 3.250.510 4.95 Acenaphthylene 0.560.051 0.85 Fluorene 0.210.051 0.32 Phenanthrene 0.500.051 0.76 Anthracene 0.100.051 0.15 Fluoranthene 0.130.051 0.20 Test-2b Pyrene 0.110.051 0.17

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57 Table 3-5. Test 2 QA/QC results % Recovery Compound LCS DLCS Test-2a Test-2b Naphthalene 77 80 NA NA Acenaphthylene 73 80 NA NA Acenaphthene 79 84 NA NA Fluorene 83 91 NA NA Phenanthrene 87 96 NA NA Anthracene 82 92 NA NA Fluoranthene 99107 NA NA Pyrene 102108 NA NA Benz[ a ]anthracene 99102 NA NA Chrysene 96 99 NA NA Benzo[ b ]fluoranthene 109109 NA NA Benzo[ k]fluoranthene 114114 NA NA Benzo[ a ]pyrene 103106 NA NA Indeno[1,2,3cd ]pyrene 107112 NA NA Dibenz[ a,h ]anthracene 112111 NA NA Benzo[ g,h,i ]perylene 114115 NA NA Fluorene-d10 99107103 97 Pyrene-d10 118128125 122

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58 Table 3-6. Tests 3 and 4 PAH concentrations and EFs Sample ID Compound Concentration (g/ft3) MRL (g/ft3) EF (mg/kg) Naphthalene ND 0.250 NA Ambient-3.4 All (excluding naphthalene) ND 0.025 NA Naphthalene 3.12 0.450 5.74 Acenaphthylene 0.43 0.045 0.80 Fluorene 0.14 0.045 0.27 Phenanthrene 0.43 0.045 0.80 Anthracene 0.08 0.045 0.15 Fluoranthene 0.12 0.045 0.22 Test-3 Pyrene 0.10 0.045 0.19 Naphthalene 5.670.370 8.07 Acenaphthylene 0.800.037 1.14 Acenaphthene 0.080.037 0.11 Fluorene 0.350.037 0.50 Phenanthrene 0.800.037 1.13 Anthracene 0.150.037 0.22 Fluoranthene 0.210.037 0.30 Pyrene 0.180.037 0.26 Benz[ a ]anthracene 0.050.037 0.07 Test-4 Chrysene 0.070.037 0.10

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59 Table 3-7. Tests 3 and 4 QA/QC results % Recovery Compound LCS DLCS Test-3 Test-4 Naphthalene 75 77 NA NA Acenaphthylene 73 78 NA NA Acenaphthene 82 86 NA NA Fluorene 87 90 NA NA Phenanthrene 94 96 NA NA Anthracene 82 85 NA NA Fluoranthene 98100 NA NA Pyrene 98 99 NA NA Benz[ a ]anthracene 92 94 NA NA Chrysene 89 94 NA NA Benzo[ b ]fluoranthene 78 79 NA NA Benzo[ k]fluoranthene 103107 NA NA Benzo[ a ]pyrene 99 99 NA NA Indeno[1,2,3cd ]pyrene 99 96 NA NA Dibenz[ a,h ]anthracene 98 98 NA NA Benzo[ g,h,i ]perylene 102101 NA NA Fluorene-d10 83 84 83 84 Pyrene-d10 95 97 94 90

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60 Table 3-8. Test 5 PAH concentrations and EFs Sample ID Compound Concentration (g/ft3) MRL (g/ft3) EF (mg/kg) Naphthalene ND 0.270 NA Ambient-5 All (excluding naphthalene) ND 0.027 NA Field Blank-5 All ND NA NA Naphthalene 9.070.450 3.94 Acenaphthylene 1.650.045 0.71 Fluorene 0.390.045 0.17 Phenanthrene 1.920.045 0.83 Anthracene 0.290.045 0.13 Fluoranthene 0.790.045 0.34 Pyrene 0.730.045 0.32 Benz[ a ]anthracene 0.120.045 0.05 Chrysene 0.170.045 0.07 Benzo[ b ]fluoranthene 0.140.045 0.06 Benzo[ k]fluoranthene 0.090.045 0.04 Benzo[ a ]pyrene 0.090.045 0.04 Indeno[1,2,3cd ]pyrene 0.070.045 0.03 Test-5a Benzo[ g,h,i ]perylene 0.070.045 0.03 Naphthalene 8.560.420 3.72 Acenaphthylene 1.270.042 0.55 Fluorene 0.310.042 0.13 Phenanthrene 1.460.042 0.63 Anthracene 0.230.042 0.10 Fluoranthene 0.550.042 0.24 Pyrene 0.510.042 0.22 Benz[ a ]anthracene 0.090.042 0.04 Chrysene 0.130.042 0.06 Benzo[ b ]fluoranthene 0.130.042 0.05 Benzo[ k]fluoranthene 0.070.042 0.03 Benzo[ a ]pyrene 0.070.042 0.03 Indeno[1,2,3cd ]pyrene 0.060.042 0.02 Test-5b Benzo[ g,h,i ]perylene 0.060.042 0.03

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61 Table 3-9. Test 5 QA/QC results % Recovery Compound LCS DLCS Test-5a Test-5b Naphthalene 73 66NA NA Acenaphthylene 67 66NA NA Acenaphthene 73 67NA NA Fluorene 75 71NA NA Phenanthrene 84 77NA NA Anthracene 79 76NA NA Fluoranthene 86 79NA NA Pyrene 84 78NA NA Benz[ a ]anthracene 90 88NA NA Chrysene 93 91NA NA Benzo[ b ]fluoranthene 95 90NA NA Benzo[ k]fluoranthene 98 98NA NA Benzo[ a ]pyrene 96 92NA NA Indeno[1,2,3cd ]pyrene 100 95NA NA Dibenz[ a,h ]anthracene 99 94NA NA Benzo[ g,h,i ]perylene 97 92NA NA Fluorene-d10 78 73 52 70 Pyrene-d10 83 76 63 75

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62 Table 3-10. Carbonyl experiment sampling conditions Date Sample ID Time (min) Sample volume (ft3) Average stack temperature (F) Qchamber (ft3/min) mburned (kg) Ambient-1 20.000.840 81234 0 Field Blank-1 20.000NA NA NA Test-1 10.000.376 353190 1.00 3/31/09 Test-1 (breakthrough) 10.000.376 353190 1.00 Ambient-2/3/4 10.000.418 77195 0 Test-2a 12.320.560 268178 1.00 Test-2b 12.320.640 268178 1.00 Test-3a 10.070.430 313174 1.00 Test-3b 10.070.480 313174 1.00 Test-4a 3.180.087 600144 1.09 5/28/09 Test-4b 3.180.078 600144 1.09 Ambient-5 5.000.309 72253 0 Field Blank-2 0.000NA NA NA Test-5a 3.800.151 145227 0.253 12/13/09 Test-5b 3.800.103 145227 0.253 Table 3-11. Test 1 carbonyl concentrations and EFs Sample ID Compound Concentration (g/m3) MRL (g/m3) EF (mg/kg) Ambient-1 All ND 13 NA Field Blank-1 All ND NA NA Formaldehyde 210028 113.4 Acetaldehyde 95028 51.1 Propionaldehyde 21028 11.3 Test-1 Valeraldehyde 4328 2.3 Test-1 (breakthrough) All ND 28 NA

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63 Table 3-12. Tests 2,3,4 carbonyl concentrations and EFs Sample ID Compound Concentration (g/m3) MRL (g/m3) EF (mg/kg) Ambient2/3/4 All ND 25 NA Formaldehyde 270019 184.7 Acetaldehyde 62019 42.4 Valeraldehyde ND19 NA Test-2a 2,5-Dimethylbenzaldehyde 15019 10.3 Formaldehyde 170017 116.3 Acetaldehyde 40017 27.4 Test-2b Valeraldehyde 2017 1.4 Formaldehyde 310025 154.6 Acetaldehyde 130025 64.8 Propionaldehyde 24025 12.0 Benzaldehyde 4425 2.2 Test-3a Valeraldehyde 5325 2.6 Formaldehyde 360022 179.5 Acetaldehyde 76022 37.9 Propionaldehyde 3022 1.5 Benzaldehyde ND22 NA Valeraldehyde 7522 3.7 Test-3b 2,5-Dimethylbenzaldehyde 81022 40.4 Formaldehyde 23000120 275.3 Acetaldehyde 14000120 167.6 Propionaldehyde 1900120 22.7 Butyraldehyde 310120 3.7 Benzaldehyde 690120 8.3 Valeraldehyde 140120 1.7 Test-4a 2,5-Dimethylbenzaldehyde 1200120 14.4 Formaldehyde 20000140 239.4 Acetaldehyde 12000140 143.6 Propionaldehyde 2000140 23.9 Butyraldehyde ND140 NA Benzaldehyde 870140 10.4 Valeraldehyde 200140 2.4 Test-4b 2,5-Dimethylbenzaldehyde 4300140 51.5

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64 Table 3-13. Test 5 carbonyl concentrations and EFs Sample ID Compound Concentration (g/m3) MRL (g/m3) EF (mg/kg) Ambient-5 All ND 34 NA Field Blank-5 All ND NA NA Formaldehyde 9000 70 873.9 Acetaldehyde 5600 70 543.8 Propionaldehyde 680 70 66.0 Benzaldehyde 81 70 7.9 Test-5a Crotonaldehyde, Total 280 70 27.2 Formaldehyde 7300100 708.9 Acetaldehyde 4500100 437.0 Propionaldehyde 940100 91.3 Benzaldehyde 120100 11.7 Test-5b Crotonaldehyde, Total 360100 35.0 Table 3-14. VOC experiment sampling conditions Date Sample ID Time (min) Average stack temperature (F) Qchamber (ft3) mburned (kg) Ambient-1/2a 3.00 88 194 0.0 Ambient-1/2b 3.00 88 194 0.0 Test-1a 2.98 252 221 0.3 Test-1b 2.98 252 221 0.3 Test-2a 2.85 253 198 0.3 6/1/09 Test-2b 2.85 253 198 0.3 Ambient-3/4 3.00 84 200 0.0 Test-3a 3.28 284 140 0.3 Test-3b 3.28 284 140 0.3 Test-4a 3.13 290 139 0.3 9/29/09 Test-4b 3.13 290 139 0.3

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65 Table 3-15. Tests 1 and 2 VOC concentrations and EFs Sample ID Compound Concentration (g/m3) MRL (g/m3) EF (mg/kg) Benzene, toluene, ethylbenzene, styrene, o -xylene ND 5 NA Ambient1/2a m,p -xylenes ND 10 NA Benzene, toluene, ethylbenzene, styrene, o -xylene ND 5 NA Ambient1/2b m,p-Xylenes ND 10 NA Benzene 3105 17.0 Toluene 955 5.2 Elthylbenzene 145 0.8 m,p -xylenes 1710 0.9 Styrene 5.35 0.3 Test-1a o -xylene 5.45 0.3 Benzene 3405 18.6 Toluene 1105 6.0 Elthylbenzene 165 0.9 m,p -xylenes 2010 1.1 Styrene 6.15 0.3 Test-1b o -xylene 6.25 0.3 Benzene 3505 18.6 Toluene 825 4.4 Elthylbenzene 145 0.7 m,p -xylenes 1110 0.6 Styrene ND 5 ND Test-2a o -xylene ND 5 ND Benzene 3005 16.0 Toluene 675 3.6 Elthylbenzene 115 0.6 m,p -xylenes ND 10 ND Styrene 135 0.7 Test-2b o -xylene ND 5 ND Table 3-16. Tests 1 and 2 LCS % recoveries Compound % recovery Acceptance limit Benzene 88 68-122 Toluene 84 74-119 Ethylbenzene 88 76-120 m,p -xylenes 89 75-120 Styrene 98 78-124 o -xylene 89 76-121

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66 Table 3-17. Tests 3 and 4 VOC concentrations and EFs Sample ID Compound Concentration (g/m3) MRL (g/m3) EF (mg/kg) Benzene, ethylbenzene, styrene, o -xylene ND 5 NA m,p -xylenes ND 10 NA Ambient3/4 Toluene 9.2 5 ND Benzene 410 5 17.8 Toluene 160 5 6.5 Ethylbenzene 25 5 1.1 m,p -xylenes 31 10 1.3 Styrene 9.6 5 0.4 Test-3a o -xylene 11 5 0.5 Benzene 350 5 15.2 Toluene 130 5 5.2 Elthylbenzene 19 5 0.8 m,p -xylenes 24 10 1.0 Styrene ND 5 ND Test-3b o -xylene 8.2 5 0.4 Benzene 330 5 13.6 Toluene 130 5 5.0 Elthylbenzene 17 5 0.7 m,p -xylenes 27 10 1.1 Styrene ND 5 ND Test-4a o -xylene 9.3 5 0.4 Benzene 360 5 14.8 Toluene 150 5 5.8 Elthylbenzene 21 5 0.9 m,p -xylenes 34 10 1.4 Styrene ND 5 ND Test-4b o -xylene 12 5 0.5 Table 3-18. Tests 3 and 4 LCS % recoveries Compound % recovery Acceptance limits Benzene 79 68-122 Toluene 84 74-119 Ethylbenzene 85 76-120 m,p -xylenes 85 75-120 Styrene 90 78-124 oxylene 87 76-121

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67 Table 3-19. Recovery study results Compound Spiked concentration (g/m3) Measured concentration (g/m3) % recovery Benzene 212 170 80 Toluene 216 170 79 Ethylbenzene 212 170 80 m,p -xylenes 416 310 75 Styrene 214 110 51 o -xylene 212 150 71 Table 3-20. PM experiment sampling conditions Date Sample ID % isokinetic Time (min) Sample volume (ft3) Average stack temp. (F) Qchamber (ft3/min) mburned (kg) Ambient-1 155 10.0 5.437 88 164 0 10/3/09 Test 1 1117.62.806 440156 1 Ambient-2 81 8.1 5.453 87 250 0 10/10/09 Test-2 96 7.02.468 317 168 1 Ambient-3 9639.1 17.20576175 0 1/14/10 Test-3 8517.710.886381152 2.384 Ambient-4 1115.0 2.02266212 0 1/27/10 Test-4 862.11.358391145 0.486 Ambient5/6 1115.02.09564145 0 Test-5 931.10.638280127 0.271 2/17/10 Tes-6 1131.00.631284116 0.201

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68 Table 3-21. PM concentrations and EFs Date/test Total filterable PM mass (g) Filterable PM concentration (g/ft3) Total CPM mass (g) CPM concentration (g/ft3) PM EF (g/kg) 10/3/09 Test 3.35E-03 1.19E -032.13E-027.60E-03 NA 10/10/09 Test NA NA 2.57E-021.04E-02 NA 11/5/09 Lab Blank NA NA 2.28E-02NA NA 11/10/09 Lab Blank NA NA 1.58E-02NA NA 1/14/10 Lab Blank NA NA 1.02E-025.95E-04 NA 1/14/10 Ambient 1.08E-03 6.28E-05NA NA NA 1/14/10 Test 2.70E-02 2.48E -031.82E-027.28E-04 2.73 1/27/10 Ambient 1.39E-03 6.87E-04NA NA NA 1/27/10 Test 7.71E-03 5.68E-03NA NA 3.17 2-17-10 Ambient 8.60E-04 4.11E-04NA NA NA 2-17-10 Test 1 2.30E-03 3.61E-03NA NA 1.60 2-17-10 Test 2 3.07E-03 4.87E-03NA NA 2.44 Table 3-22. EC/OC experiment sampling conditions Sample Sample date Sample volume (ft3) Average stack temp. (F) Qchamber (ft3/min) Sample time (min) mburned (kg) Ambient-1 12/10/09 3.99 61 NA 10.00 0 Test-1 12/10/09 1.94 156 2073.50 0.5 Ambient-2/3 12/11/09 6.09 51 NA 10.00 0 Test-2 12/11/09 2.59 240 1873.70 0.5 Test-3 12/11/09 2.54 186 2074.38 0.5

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69 Table 3-23. OC and EC concentrations and EFs Concentration on filter Concentration in air EFs Sample OC (g/2.7 cm2) EC (g/2.7 cm2) OC (g/ft3) EC (g/ft3) OC (g/kg) EC (g/kg) Lab Blank 2.2 0NA NA NA NA Ambient-1 6.4 012.880.00 NA NA Test-1 60.6 154.1250.23636.16 0.35 0.93 Ambient-2/3 8.4 011.040.00 NA NA Test-2 39.3 176.8121.41546.63 0.15 0.76 Test-3 37.4 124.1118.03391.20 0.19 0.71 Figure 3-1. Uniformity test data

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70 Figure 3-2. Flue gas concentrations and MCE (Note: dashed line represents when th e flame was extinguished

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71 CHAPTER 4 DISCUSSION EF summary Table 4-1 summarizes the average and standar d deviat ion of the speciated EFs in addition to the 95% confidence interval (calculated using t values) for the dry and whole stalk experiments separately fo r all the pollutants quantified in this study. A detailed analysis of the emission and trends for each pollu tant class are further provided in the following sections. PAHs PAH emiss ions were dominated by lower molecular weight compounds (i.e., two and three ring PAH compounds). In fact, napht halene (2-ringed) contributed to 66% of the overall EF, on average. 3-ring PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene) contri buted to 27% of the total PAH EF and 4-ring PAHs (fluoranthene, pyrene, benzo[a] anthracene and chrysene) contri buted to 8% of the total EF, on average. The total PAH EF for dry leaf experiments was 7.13 0.94 mg/kg. This EF does not include any emissions of heavier molecular weight compounds, which were below detection limits in these experiments. The whol e stalk EF was slightly higher than dry leaf experiments.18 3.26 mg/kg. Figure 4-1 compares EFs determined in th is study to EFs determined by Jenkins et al. (1996b) for all PAH compounds excluding naphthalene, since naphthalene EFs were marked as questionable by Jenkins et al (1996b) due to high blank concentrations in their QA/QC samples. Figure 4-2 show s a comparison of sugarcane PAH EFs and EFs determined by Hays et al. (2002) for fo liar fuels (including naphthalene). It should be noted that Hays et al. (2002) quantified particulate and gaseous PAH compounds

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72 separately; therefore, the figure only compares compounds that are known to exists mainly in the gas-phase (i.e., low molecular weight compounds). Sugarcane EFs are comparable, but lower than Jenkins et al. (1996b) for agricultural residue. The relative abundance of acenaphthylene and phenanthrene is consistent for all fuel types. Hays et al. (2002) PAH EFs are much higher than t he EFs determined in this study, but again the abundance of naphthalene a nd acenaphthylene are consistent between these studies. The lower EFs exhibited in this study are likely due to the high MCE observed in this study (~99%). Since PAH compounds (as well as other pollutant emissions) form as a result of incomplete combustion, it is expected that po llutant emissions will decrease with increasing combustion efficiency. PAH concentrations in whole stalk experim ents were slightly higher than dry leaf experiments. As other studies have dem onstrated, MC has an important impact on emissions (Hays et al., 2005; McMeeking et al., 2009; Simoneit, 2002). Generally, higher MCs inhibit ideal combustion by lo wering the temperature and CE, leading to higher pollutant emissions. However, at ve ry low moisture contents the biomass burns quickly, creating oxygen-limited conditions leading to a decrease in the CE. In addition to CE, PAH formation is very sensitive to temperaturePAH formation is supported at high temper atures (in excess of 500 C) (Conde et al., 2005). While higher MC fuels may exhibit lower CEs, they also will likely have a lower combustion temperature, possibly inhibiting PAH formati on. This may explain why whole stalk PAH EFs were only slightly higher than dry leaf EFs. It is apparent t hat there are numerous factors that impact emissions and these impacts are not always straightforward.

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73 As naphthalene consistently comprises a large portion of the PAH emissions, it may serve as a good indicator of the total PAH concentration. Conde et al. (2005) found a strong relationship between the total PAH concentration and the naphthalene concentration. Naphthalene is one of the fi rst PAH compounds formed and is one of the most stable. It also serves as a building block for further PAH formation, making it a good indicator of total PAH fo rmation (Conde et al., 2005). In the present study, strong relationships were found between naphthalene (r2=0.99), acenaphthylene (r2=0.98) and phenanthrene (r2=0.98) concentrations and the total PAH concentration. Figure 4-3 shows the relationships between individual compound concentrations and the total PAH concentration. The same analysis was perfo rmed for individual PAH compound EFs compared to the total PAH EF, and a similar result was found (Figure 4-4). These findings suggest that measuring a few select PAH compounds could infer the total PAH emissions from a particular source, ther eby simplifying sampling and analytical procedures. Organic compounds, like PAHs, can serve as source markers in apportionment studies (Yang et al., 2006; Schauer et al., 2001). Certain compounds can be used as specific tracers (e.g., levoglucosan) or compound ratios or patterns can be used to identify specific sources. A num ber of helpful ratios were i dentified in this study, which could serve as source information for fu ture source apportionment studies. The concentration ratio of fluoranthene to pyrene was on average 1.15 in all experiments. The ratio of phenanthrene/acenapthylene was 1.0 and the ratio of indeno[1,2,3cd]pyrene/(indeno[1,2,3-cd)pyr ene+benzo[ghi]perylene) was 0.475. These ratios as well as some from other studies for other sources are compared in Table 4-2. The

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74 differences between these ratios and the ratios of other sources can be helpful when apportioning emissions to specific sources (Ravindra et al., 2008). Carbonyls The mean carbonyl EFs were 231.8 52.3 mg/kg and 909.6 527.7 mg/kg for dry leaf and whole stalk experiment s, respectively. In all experiments, formaldehyde was the most dominant carbonyl compound account ing for over 50% (ranged from 51-78%) of quantified carbonyl emissions. Acetal dehyde was the second most abundant compound followed by propional dehyde. Other compounds detected, in much lower concentrations, were butyraldehyde, benzaldehyde, valeraldehyde and 2,5dimethylbenzaldehyde. Cr otonaldehyde was only detected in the 12/13/09 experiment, which also exhibited the highest EFs. As with the dominant PAH compounds, fo rmaldehyde and acetaldehyde EFs were highly correlated with the total PAH EF. Figu re 4-5 shows the relationships, which had r2 values of 0.991 and 0.996 for formaldehyde and acetaldehyde, respectively. Figure 4-6 shows the correlations between formaldehyde and acetaldehyde concentrations and the total carbonyl concentration, which also exhibited excellent correlation. Because of their high correlation, formaldehyde and acetald ehyde could serve as predictor compounds for total carbonyl emissions. EFs from whole stalk experiments exhibi ted considerably higher EFs for most compounds (except valeraldehyde) than for dry leaf experiments. The ratio of whole stalk EFs to dry stalk EFs r anged from 0.8 (valeraldehyde) to 7.2 (acetaldehyde). The 12/13/09 whole stalk experiment had much hi gher EFs than the 5/ 28/09 whole stalk experiment. In additi on to the differences in the biomass source (collected at different

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75 times and from different field locations), the two experiments had markedly different burning conditions. The fire of the 5/28/09 experiment was much more intense than the fire of the 12/13/09 experim ent. The average temperat ure of the former was 600 F and 1 kg of biomass burned in 3 minutes, whereas in the later experiment only 256 g of biomass burned in 3 minutes and t he average temperature was around 145 F. The different burning conditions were a result of di fferent initial loading conditions (i.e., how much sugarcane was initially loaded) and operator differences (i.e., how the researcher fed the biomass into the chamber). The differences in the EFs can be attributed to these differences in the burning conditions. T he more intense fire had more complete combustion as compared to the lower te mperature fire, which exhibited more smoldering combustion. The difference between carbonyl whole stalk and dry leaf EFs is more significant than PAH EFs for the two experimental conditions This can be attributed to the fact that PAH EFs are very sensitive to temperat ure in addition to CE, whereas carbonyl EFs may be less dependent on temperatur e. It should also be noted that tests 4 and 5 (for both carbonyls and PAHs) used biomass from di fferent sources. Ther efore, in addition to the differences in burning conditions and MC, the biomass composition, condition, and treatment practices (which differed for t he different growing areas) may have also influenced the EFs. Figure 4-7 compares the carbonyl EFs to crop residue burned in a cookstove (Zhang et al., 1999) and foliar fuels (Hays et al., 2002). The dry sugarcane EFs are lower than EFs determined for foliar fuels, but agree well with those of crop residue burned in a cookstove. The EFs for whole stal ks agree well with those of the foliar fuels

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76 for formaldehyde, acetaldehyde and crotonaldehyde compounds. Formaldehyde followed by acetaldehyde and propionaldehyde we re the most dominate compounds in all studies. Hedberg et al. (2002) discussed using the ratio of formaldehyde to acetaldehyde for source characterization. They reported an average ratio of 5 (range: 3.3-8.8) for birch wood burning in a wood stove. In this study the average ratio was 2.7 with a range of 1.6 to 4.7, which is very similar to a ra tio of 3 obtained for moto r vehicle emissions by Johansson et al. (2001). This highlights t hat carbonyl compound ratios may not be helpful in identifying emissions from spec ific sources. It should also be noted that formaldehyde and acetaldehyde compounds are formed in the atmosphere through the photochemical oxidation of organic com pounds, further emphas izing that these compounds are not suitable as source markers. VOCs First, it should be emphasized that the EFs presented here may underestimate the true EFs because of sampling los ses observed. According to the recovery study, the concentrations may be underestimated by a pproximately 20% for benzene, toluene and ethylbenzene, 25% for m,p -xylene, 29% for o -xylene and 49% for styrene. Samples loss in Tedlar bags is a documented problem fo r this type of sampling (Kumar and Viden, 2007). Overall, the experiments had very consist ent results. In all experiments, benzene was the most prominent compound quantifi ed, accounting for an average of 69% (ranged between 63-77%) of emissions. Tol uene accounted for an average of 22% (ranged between 17-25%) of VOC emissions. The relative abundance of benzene and toluene as the dominant aromatics is consist ent with other biomass combustion studies

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77 (Hays et al., 2002) The other compounds we re present in much lower fractions m,p xylenes, ethylbenzene, o -xylene and styrene accounted, on average, for 4%, 3%, 2% and 1% of VOC emissions, respectively. However, it is likely styrene accounts for a larger fraction, but in this experiment it exhi bited a significantly lower recovery efficiency as compared to the other compounds. VOC EFs are significantly lower than those determined by Hays et al. (2002) for foliar fuels, but are similar with those det ermined by Jenkins et al. (1996a) for almond and walnut prunings. A comparison of the EFs determined in this study and Jenkins et al. (1996a) are presented in Figure 4-8. Yoke lson et al. (2008) presented VOC EFs for sugarcane based on one experiment that used proton-transfer reaction mass spectrometry (PTR-MS), a real-time measurem ent technique. Yokelson et al.s (2008) VOC EFs significantly higher than the EFs determined in this study and are on par to Hays et al. (2002). Table 4-3 summarizes the comparison. Hedberg et al. (2002) suggested compar ing ratio of toluene to benzene to discriminate between various sources. They found an average ratio of 0.4, which is very similar to the ratio determined in this study.32. The low toluene to benzene is quite different from the ratio determined by Johannson et al. (2001) for vehicle exhaust.6, which may make this a usef ul ratio to differentiate between biomass burning and vehicular exhaust emissions in source apportionment studies. PM2.5 The mean PM2.5 EF was 2.49 0.66 g/kg, based on dry l eaf experiments. The EF is in excellent agreement with the PM2.5 EF for sugarcane determined by Yokelson et al. (2008) and is within the range of the current published PM EF for sugarcane pre-harvest

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78 burning (USEPA, 1995). The sugarcane PM2.5 EF also agrees with other biomass materials such as wheat straw (Dhammapala et al., 2007b; Hays et al., 2005) and rabbitbrush (McMeeking et al., 2009), but is lower than EFs determined for rice straw (Hays et al., 2005) and other foliar fuels, wh ich are not presented in Table 4-4 (Hays et al., 2002; McMeeking et al., 2009). EC and OC There are a few uncertainties with EC/OC sampling and analysis that should be mentioned. Namely, the OC sampling arti facts and the different methods used for carbon measurements. Accurate OC samp ling is complicated by both positive and negative artifacts, which are attributed to OCs volatility. During sampling, some gaseous organic compounds may absorb on the filt er surface or onto collected particles, resulting a positive artifact. In contrast, OC particles collected on the filter may vaporize and be lost during sampling or during the stor age (negative artifact). Since the sampling time was very short in this study (less t han 5 minutes), the magnitude of the negative and positive OC artifacts is expected to be low. However, a definite positive OC artifact was observed from the presence of OC in both the laboratory and ambient blank samples, but was accounted for in determining the OC EF. Different studies account for these artifacts in various ways. The second uncertainly in OC/EC determi nations is the analytical method used. Two methods are currently used: the Inte ragency Monitoring of Protected Visual Environments (IMPROVE) protocol and N IOSH Method 5040. The methods differ in their temperature profile protocols (i.e., the timing and set points of the heating sequence) and in the technique used to correct for OC that is pyrolized into EC during the analytical sequence (IMPROVE method uses reflectance whereas the NIOSH

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79 method uses transmittance). Due to the majo r differences in these methods, EC and OC concentrations are currently operational ly defined by the analytical technique used and results from the two techniques may differ significantly (Chow et al., 2001; McMeeking et al., 2009). The different anal ytical techniques used should be accounted for when reporting and comparing OC and EC data. In this study, the average EFs for OC and EC were 0.23 0.102 g/kg and 0.80 0.115 g/kg, respectively. The concentration ratio of OC to EC was 0.31 0.086 and the EF ratio of OC to EC was 0.28 0.086. The high EC relative to OC ratio found in this study is very unique for biomass burning. OC dominates EC in most biomass burning emissions; however, a few exceptions have been reported (McMeeking et al., 2009). Table 4-5 compares the EC and OC EFs determi ned in this study to other biomass fuels (which were analyzed by the same met hodNIOSH 5040). Sugarcane OC EFs are on the low end of other reported EFs, whereas EC EFs are on the high end. McMeeking et al. (2009) tested a wide range of biomass materials and found a negative correlation between the MCE and OC EFs (r2=0.36). They found that leafy fuels, which had lower MCEs, exhibited the highest OC EFs. EC EFs increased with increasing CE, particularly for MCE>93%; however, ECs dependence on MCE was not as strongly correlated as in the case of OC (r2=0.09). Instead, EC and other inorganic emissions were found to be a stronger f unction of the fuel type and composition. Nonetheless, the high EC rela tive to OC emissions from sugarcane burning can be partially attributed to the high MCE observed in this study and may also be a function of the biomass composition. The characteristic EC/OC ratio may be useful in future source apportionment studies to identify and quantify c ontributions from sugarcane burning.

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80 HAP Emission Estimates The total yearly emissions of the HAPs in v estigated in this study were estimated based on the EFs determined. The emissions were then compared to the 2005 national emission inventory to estimate the relative importance of this practice to PBC and Floridas emission inventories (USEPA, 2010). The yearly emissions were calculated a ssuming 335,650 acres of sugarcane were burned and a fuel loading of 7 tons/acre. Emissions were estimated considering both dry leaf and whole stalk EFs. EFs were tak en as the upper limit of the 95% confidence interval for the range of EFs determined for each category. Table 4-6 summarizes the EFs used and the total emissions for eac h pollutant and Table 4-7 summarizes the contribution of sugarcane field burning to t he emission inventories. Tables 1 and 2 only present data for pollutants reported in the nat ional emission inventory, although some other pollutants were studied in this project (e.g., PM2.5). As shown in Table 4-7, sugarcane field burning did not contribute substantially (<5%) to VOC compounds in PBC, and thus t heir state contribution was not estimated. VOC emissions were dominated by gasoline sources (on-road and non-road equipment). Sugarcane field burning also did not contribute significantly to naphthalene emissions in PBC and Florida. Howeve r, sugarcane field burning contributed substantially to emissions of other PAH compounds and carbonyl compounds. Based on dry leaf EFs, sugarcane field burning contributions ranged from 44-64% for PBC PAH emissions and 51-56% for carbonyl emissions. Based on whole stalk EFs, sugarcane field burning contributions ranged from 23-78% for PBC PAH emissions and 86-91% for PBC carbonyl compound emissions.

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81 Sugarcane field burning is also an impor tant source for ce rtain PAH and carbonyl compounds in the Florida stat e emission inventory. On the state level, sugarcane burning (using whole stalk EFs) contri buted to over 10% of emissions for acenaphthylene, fluorene, and benzo(b)fl uoranthene compounds. Emission contributions for carbonyl compounds were even greater, 29 and 37% for formaldehyde, acetaldehyde and propionaldehyde compounds, respectively. Using the dry leaf EFs, contributions range from 1-8% for these compounds. Since a large amount of biomass is burned in the localized area of PBC and any biomass combustion produces PAH and carbony l compounds, it is expected that the emissions from this source will be a majo r contributor to the local emissions. Table 4-1. EF summary Dry leaves Whole stalks Compound Mean std. dev. 95% confidence interval Mean std. dev. 95% confidence interval PAHs (mg/kg) 7.13.947.13 1.48 8.18.26 8.18.10 Naphthalene 4.83.724.83.145. 24.45 5.24.10 Acenaphthylene 0.78.090.78.140. 80.30 0.80.75 Acenaphthene ND NA 0.11 NA Fluorene 0.26.050.26.080. 27.20 0.27.50 Phenanthrene 0.73.100.73.160. 87.25 0.87.63 Anthracene 0.14.030.14.050. 15.06 0.15.15 Fluoranthene 0.20.020.20.030. 30.05 0.30.13 Pyrene 0.18.010.18.020. 27.05 0.27.12 Benz[ a ]anthracene ND NA 0.05.01 0.05.04 Chrysene ND NA 0.08.02 0.08.05 Benzo[ b ]fluoranthene ND NA 0.06.00 0.06.01 Benzo[ k]fluoranthene ND NA 0.03.01 0.03.02

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82 Table 4-1. Continued Dry leaves Whole stalks Compound Mean std. dev. 95% confidence interval Mean std. dev. 95% confidence interval Benzo[ a ]pyrene ND NA 0.04.01 0.04.01 Indeno[1,2,3cd ]pyrene ND NA 0.03.00 0.03.01 Benzo[ g,h,i ]perylene ND NA 0.03.00 0.03.01 Carbonyls (mg/kg) 201.2201.5942 942.3 Formaldehyde 150.8150524 524 Acetaldehyde 44.8.1 44.8323 323 Propionaldehyde 8.3.98 .3.351.0.6 51.0 Butyraldehyde ND NA 3.7 NA Benzaldehyde 2.2 NA 9.6.8 9.6.8 Valeraldehyde 2.5.22 .5.42.1.5 2.1.8 2,5-Dimethylbenzaldehyde ND NA 33.0.2 33.0.7 Crotonaldehyde, Total ND NA 31.1.5 31.1.7 VOCs (mg/kg) 23.9.6223.9.89 NA NA Benzene 16.5.8916.5.58 NA NA Toluene 5.2.945.2.79 NA NA Ethylbenzene 0.8.150.8.12 NA NA m,p -Xylenes 0.9.450.9.38 NA NA Styrene 0.3.250.3.21 NA NA o -Xylene 0.3.190.3.16 NA NA Particulate matter (g/kg) PM2.5 2.5.662.5.1 NA NA EC 0.23.10 0.23.26 NA NA OC 0.80.12 0.80.29 NA NA Table 4-2. Signature PAH compound ratios Ratio Sugarcane burning Carsa Diesela Wood burninga Indeno[1,2,3 cd ]pyrene/(indeno[1,2,3cd ] pyrene+benzo[ ghi]perylene) 0.480.180.37 0.62 Phenanthrene/acenaphthylene 1.00NA NA NA Fluoranthene/pyrene 1.150.60NA NA aRavindra et a., 2008

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83 Table 4-3. VOC EF (mg/kg) comparison Compound Sugarcane Sugarcanea Florida palm and slash pineb Wheatc Benzene 16.5 207 168.5 145 Toluene 5.2 120 145.5 77 Elthylbenzene 0.8 60 20.2 NA m,pXylenes 0.9NA 54.5 NA Styrene 0.4NA 19.0 91 o -Xylene 0.3NA 15.0 NA aYokelson et al., 2008, bHays et al., 2002, cJenkins et al., 1996a Table 4-4. PM EF (g/kg) comparison Other references Sugarcane PM2.5 Sugarcane PMa Sugarcane PM2.5 b Wheatc Wheat strawd Rice strawd Rabbitbrushe 2.49 0.66 2.3-3.5 2.17 3.0.64.71.04 12.950.30 3.4 a USEPA, 1995, bYokelson et al., 2008, cDhammapala et al., 2007, dHays et al., 2005, eMcMeeking et al., 2009 Table 4-5. EC and OC EF comparison Other references Sugarcane Wheata Wheatb Riceb Rabbitbrushc OC (g/kg) 0.23 0.102 1.9.1 (CE 94.2%) 1.23.038.94.42 0.5 (MCE~95.6%) EC (g/kg) 0.80 0.115 0.35.16 (CE 96.1%) 0.52.000.17.04 1.4 (MCE~95.6%) aDhammapala et al., 2007 (modified NIOSH), bHays et al., 2005 (NIOSH), cMcMeeking et al., 2009 (modified NIOSH)

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84 Table 4-6. Emission factors and yearly emissions for sugarcane field burning EF (upper 95% confidence limit) Yearly emissions (tons) Compound Dry leaves Whole st alks Dry leaves Whole stalks PAHs (mg/kg) Naphthalene 5.9711.3414.027 26.644 Acenaphthylene 0.921.552.162 3.642 Acenaphthene NA 0.11NA 0.258 Fluorene 0.340.770.799 1.809 Phenanthrene 0.891.502.091 3.524 Anthracene 0.190.300.446 0.705 Fluoranthene 0.230.430.540 1.010 Pyrene 0.200.390.470 0.916 Benz[ a ]anthracene NA 0.09NA 0.211 Chrysene NA 0.13NA 0.305 Benzo[ b ]fluoranthene NA 0.07NA 0.164 Benzo[ k]fluoranthene NA 0.05NA 0.117 Benzo[ a ]pyrene NA 0.05NA 0.117 Indeno[1,2,3cd ]pyrene NA 0.04NA 0.094 Benzo[ g,h,i ]perylene NA 0.04NA 0.094 Carbonyls (mg/kg) Formaldehyde 192.0 1027.0 451.1 2413.0 Acetaldehyde 62.8 639.0 147.6 1501.3 Propionaldehyde 15.6 104.0 36.7 244.4 VOCs (mg/kg) Benzene 18.1 NA 42.5 NA Toluene 6.0 NA 14.1 NA Elthylbenzene 0.9 NA 2.2 NA m,p -Xylenes 1.3 NA 3.0 NA Styrene 0.5 NA 1.2 NA o -Xylene 0.5 NA 1.1 NA

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85 Table 4-7. Contribution of sugarcane fiel d burning to annual emissions in PBC and Florida Contribution to emissions (%) Compound PBC (dry leaves) PBC (whole stalks) Florida (dry leaves) Florida (whole stalks) PAHs (mg/kg) Naphthalene 0.91.70.7 1.3 Acenaphthylene 56.969.06.7 10.8 Acenaphthene NA 52.3NA 6.2 Fluorene 60.877.88.3 17.0 Phenanthrene 63.774.75.9 9.5 Anthracene 58.068.62.3 3.6 Fluoranthene 54.268.92.0 3.7 Pyrene 44.260.71.3 2.5 Benz[ a ]anthracene NA 50.10.0 1.0 Chrysene NA 66.6NA 1.5 Benzo[ b ]fluoranthene NA 77.0NA 11.0 Benzo[ k]fluoranthene NA 61.0NA 1.4 Benzo[ a ]pyrene NA 62.40.0 2.1 Indeno[1,2,3cd ]pyrene NA 53.7NA 0.9 Benzo[ g,h,i ]perylene NA 22.6NA 0.6 Carbonyls (mg/kg) Formaldehyde 53.486.03.3 15.5 Acetaldehyde 51.291.43.8 28.7 Propionaldehyde 56.189.58.0 36.6 VOCs (mg/kg) Benzene 3.2NA ND NA Toluene 0.5NA ND NA Elthylbenzene 0.4NA ND NA Styrene 1.6NA ND NA o,m,p -xylene (mixture 1.8NA ND NA

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86 Figure 4-1. Comparison of PAH EFs to Jenkins et al., 1996b

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87 Figure 4-2. Comparison of PAH EFs to Hays et al., 2002

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88 Figure 4-3. Total PAH concentration as a function of individual PAH concentrations

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89 Figure 4-4. Total PAH EF as a function of individual PAH EFs

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90 Figure 4-5. Total carbonyl EF as a function of individual carbonyl EFs

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91 Figure 4-6. Total carbonyl concentration as a function of individual carbonyl concentration

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92 Figure 4-7. Comparison of carbonyl EFs

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93 Figure 4-8. Comparison of VOC EF

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94 CHAPTER 5 SUMMARY AND CONCLUSIONS This study further characterized the em issions from the pre-harvest burning of sugarcane fields. EFs were determined for a number of HAPs inc luding PAH, carbonyl and VOC compounds as well as PM2.5, OC and EC in a combustion chamber. In addition to quantifying EFs, spec ific compound patterns were identified, which can help in source apportionment studies and emission estimates. In general, EFs were consistent between experiments and comparable to other published emission factors for sugarcane bur ning and other agricultural materials considering the differences in biomass composition, biomass source, and burning conditions. Consistent with previous similar studies, our experiment s show that EFs are strongly impacted by burning conditions (t emperature, intensit y, fuel density, combustion efficiency) and bi omass properties (moisture content, composition). For example, experiments that used higher moisture content biomass (i.e., whole stalks) exhibited higher EFs. Also, mo re intense fires (characterized by higher fuel loading and temperatures) produced lower EFs. It should be emphasized that field burning is characterized by numerous burning phases (i.e., smoldering, flaming) and is influenced by a number of variables (meteorological conditions, plant conditions, plant treatment, ect.). EFs are expected to be highly variable during the field burning proc ess as well as highly variable during the harvesting periodas the meteorological and plant conditions will change drastically throughout the harvesting season. The EFs reported in this study are most representative of the flaming phase of co mbustion and may be a conservative estimate

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95 of emissions, since previous studies have s hown that smoldering combustion exhibits significantly higher emissions (Jenkins et al., 1996b). The data from this research will allo w the EPA to validate and expand the EFs published in AP-42 for sugarcane pre-harvest burning. The EFs can be used to more accurately calculate the annual emissions from sugarcane pre-harvest burning to evaluate the contribution of this source to local and state pollutant inventories. In addition, these data can be used in the National-Scale Air Toxics Assessment (NATA) to help identify important air toxic exposur e sources with the goal of protecting public health. With more reliable data, regulatory a gencies are able to more accurately model human and environmental exposure and to subsequently make better management and permitting decisions.

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96 LIST OF REFERENCES Carrico, C.M., Petters, M.D., Krei denweis, S.M., Collett, J.L., Engling, G., Malm, W.C., 2008. Aerosol hygroscopicity and cl oud droplet activation of extracts of filters from biom ass burning experiments. Journal of Geophysical Research 113, D08206, doi:10.1029/2007JD009274. Chen, L.-W., Moosmller, H., Arnott, W. P., Chow, J.C., Watson, J.G., Susott, R.A., Babbitt, R.E., Wold, C.E., Lincol n, E.N., Hao, W.M., 2007. Emissions from laboratory combustion of wildland fuels: emission factors and source profiles. Environmental Science and Technology 41, 4317-4325. Chow, J.C., Watson, J.G. Crow, D., Lowenthal, D.H ., Merrifield, T., 2001. Comparison of IMPROVE and NIOS H Carbon Measurements. Aerosol Science and Technology 34, 23-34. Conde, F.J., Ayala, J.H., Afonso, A.M. Gonzlez, V., 2005. Emissions of polycyclic aromatic hydrocarbons from combustion of agricultural and sylvicultural debris. Atmospheric Environment 39, 6654-6663. Crutzen, P.J. and Andreae, M.O., 1990. Biomass burning in the tropics: impact on atmospheric chemistry and biogeochemical cycles. Science 250, 16691678. Darley, E.F. and Lerman, S.L., 1975. Air pol lutant emissions from burning sugar cane and pineapple residues from Hawa ii. Environmental Protection Agency Grant No. R800711, University of California, Riverside, CA. Available online at: http://www.epa.gov/ttn/chief/old/ap42/c h09/s1011/reference/ref02_c09s10 11_jan1995.pdf Dhammapala, R., Claiborn, C., C orkill, J., Gullett, B., 2006. Particulate emissions from wheat and Kentucky bl uegrass stubble burning in eastern Washington and northern Idaho. At mospheric Environment 40, 10071015. Dhammapala, R., Claiborn, C., Jimenez, J. Corkill, J., Gullett, B., Simpson, C., Paulsen, M., 2007a. Emission fa ctors of PAHs, methoxyphenols, levoglucosan, elemental carbon and or ganic carbon from simulated wheat and Kentucky bluegrass stubble burns. Atmospheric Environment 41, 2660-2669. Dhammapala, R., Claiborn, C., Simps on, C., Jimenez, J., 2007b. Emission factors from wheat and Kentucky bluegrass stubble burning: Comparison of field and simulated burn experim ents. Atmospheric Environment 41, 1512-1520.

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97 Gullett, B.K., Touati, A., Huwe, J., Hakk, H., 2006. PCDD ad PCDF emissions from simulated sugarcane field burning. Environmental Science and Technology 40, 6228-6234. Gupta, P.K., Prasad, V.K., Sharma, C. Sarkar, A.K., Kant, Y., Badarinath, K.V.S., Mitra, A.P., 2001. CH4 Emissions from biomass burning of shifting cultivation areas of tropi cal deciduous forests-experimental results from ground-based measurements. Chemosphere 3, 133-143. Hays, M.D., Fine, P.M., Geron, C.D., Kleeman, M.J., Gullett, B.K., 2005. Open burning of agricultural biomass: ph ysical and chemical properties of particle-phase emissions. Atmos pheric Environment 39, 6747-6764. Hays, M.D., Geron, C.D., Linna, K.J., Sm ith, N.D., 2002. Speciation of gas-phase and fine particle emissions from burn ing of foliar fuels. Environmental Science and Technology 36, 2281-2295. Habib, G., Venkataraman, C., Bond, T.C., Schauer, J.J., 2008. Chemical, microphysical and optical properties of primary parti cles from the combustion of biomass fuels. Environmental Science and Technology 42, 8829-8834. Hedberg, E., Kristensson, A., Ohlsson, M., Johansson, C., Johansson, P.A., Swietlicki, E., Vesely, V., Wideqvist, U., Westerholm, R., 2002. Chemical and physical characterization of emissi ons from birch wood combustion in a wood stove. Atmospheric Environment 36, 4823-4837. Jenkins, B.M., Turn, S.Q., Williams, R. B., Goronea, M., Ad b-el-Fattah, H., Mehlschau, J., Raubach, N., Chang, D.P.Y., Kang, M., Teague, S.V., Raabe, O.G., Campbell, D.E., Cahill, T. A., Pritchett, L., Chow, J., Jones, A.D., 1996a. Atmospheric pollutant emi ssion factors from open burning of agricultural and forest biomass by wi nd tunnel simulations, Vol. 1-3. California Air Resources Board Project No. A932-126, University of California, Davis, CA. Available online at: http://www.arb.ca.gov/ei/spec iate/ r01t20/rf9doc/refnum9.htm Jenkins, B.M., Jones, A.D., Turn, S.Q., Williams, R.B., 1996b. Emission factors for polycyclic aromatic hydrocar bons from biomass burning. Environmental Science and Technology 30, 2462-2469. Johansson, C., Wideqvist, U., Hedber, E., Vesely, V., 2001. ITM-Institute of Applied Environmental Science ISSN 1103-341X. Stockholm University, Stockholm, Sweden. Kirchhoff, V.W.J.H., Marinho, E.V.A., Dias, P.L.S., Pereira, E.B., Calheiros, R., Andre, R., Volpe, C., 1991. Enhancements of CO and O3 from burnings in sugar cane fields. Journal of Atmospheric Chemistry 12, 87-102.

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98 Kumar, A., and Viden, I., 2007. Volat ile organic compounds: sampling methods and their worldwide profile in ambient air. Environmental Monitoring Assessment 131, 301-312. Langmann, B., Duncan, B., Textor, C., Tr entmann, J., van der Werf, G.R., 2009. Vegetation fire emissions and their im pact of air pollution and climate. Atmospheric Environment 43, 107-116. Lara, L.L., Artazo, P., Mart inelli, L.A., Camargo, P.B ., Victoria, R.L., Ferraz, E.S.B., 2005. Properties of aerosols fr om sugar-cane burning emissions in Southeastern Brazil. Atmospher ic Environment 39, 4627-4637. Lemieux, P.M., Lutes, C.C., Santoianni, D.A., 2004. Emissions of organic air toxics from open burning: a comprehens ive review. Progress in Energy and Combustion Science 30, 1-32. Liu, Y., Shao, M., Fu, L., Lu, S., Zhen, L., Tang, D., 2008. Source profiles of volatile organic compounds (VOCs) measured in China: Part I. Atmospheric Environment 42, 6247-6260. McMeeking, G.R., Kreidenweis, S.M., Ba ker, S., Carrico, C.M., Chow, J.C., Collett, J.L., Hao, W.M., Holden, A. S., Kirchstetter, T.W., Malm, W.C., Moosmller, H., Sullivan, A.P., Wold C.E., 2009. Emissions of trace gases and aerosols during the open combustion of biomass in the laboratory. Journal of Geophysical Research 114, D19210. doi:10.1029/2009JD011836. Meyer, M.C., Mueller, J.F., Beer, T., Marney, D., Bradbury, G., 2004. Field and laboratory based emission factors for PCDD/CDF/PCB from sugarcane fires. Organohalogen Compounds 66, 928-934. Mitra, A.P., Morawska, L., Sharma C., Zhang, J., 2002. Chapter two: methodologies for characterisati on of combustion sources and for quantification of their emissi ons. Chemosphere 49, 903-922. Na, K. and Cocker, D.R., 2008. Fine organic particle, formaldehyde, acetaldehyde concentrations under and after the influence of fire activity in the atmosphere of Riverside, Californ ia. Environmental Research 108, 714. National Institute for Occupation Safety and Health (NIOSH), 1999. Method 5040 Issue 3 (Interim): elemental carbon (diesel exhaust). NIOSH Manual of Analytical Methods. National Institut e of Occupation Safety and Health, Cincinnati, OH.

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99 National Agricultural Statistics Serv ice (NASS), 2009. Hawaii Sugarcane Acreage and Production. Available online at: http://www.nass.usda.gov/Statistics_by _State/Hawa ii/Publications/Sugarc ane_and_Specialty_ Crops/sugar.pdf Palm Beach County Health Department 2006 Emission Inventory. Prepared by Palm Beach County Health Department. Obtained from James_Stormer@doh.state.fl.us. Pedersen, D.U., Durant, J.L., Taghizadeh, K., Hemond, H.F., Lafleur, A.L., Cass, G.R., 2005. Human cell mutagens in resp irable airborne particles from the Northeastern United States. 2. Quant ification of mutagens and other compounds. Environmental Scienc e and Technology 39, 9547-9560. Ravindra, K., Sokhi, R., Grieken, R.V. 2008. Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factor s and regulation. Atmospheric Environment 42, 2895-2921. Reuters, 2007. Brazil sugar cane mills agree to end bur ning by Available online at: http://www.reuters.com/ar ticle/idUSN224 5768620071022 Rogge, W.F., Zhang, Z., Yan, Y., 1998. Characteristics of seasonal sizesegregated particle concentrations (P M10) at Belle Glade and Delray Beach, Florida. Prepared for Palm Beach County Health Department. Russell, A.G. and Brunekreef, B., 2009. A focus on particulate matter and health. Environmental Science and Technology 43, 4620-4625. Schauer, J.J., Kleeman, M.J., Cass, G.R. Simoneit, B.R.T., 2001. Measurement of Emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood. Environmental Science and Technology 35, 1716-1728. Simoneit, B.R.T., 2002. Biomass burninga review of organic tracers for smoke from incomplete combustion. App lied Geochemistry 17, 129-162. Tissari, J., Lyyrnen, J., Hytnen, K., Sippul a, O., Tapper, U., Frey, A., Saarnio, K., Pennanen, A.S., Hillamo, R., Salonen, R.O., Hirvonen, M.-R., Jokiniemi, J., 2008. Fine particule and gaseous emissions from normal and smouldering wood combustion in a conventional masonry heater. Atmospheric Environment 42, 7862-7873. Tsai, S.M., Zhang, J., Smit h, K.R., Ma, Y., Rasmuss en, R.A., Khalil, M.A.K., 2003. Characterization of non-me thane hydrocarbons emitted from various cookstoves used in China. Environmental Science and Technology 37, 2869-2877.

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100 Turn, S.Q., Jenkins, B.M., Chow, J.C., Pr itchett, L.C., Campbell, D., Cahill, T., Whalen, S.A., 1997. Elemental charac terization of particulate matter emitted from biomass burning: Wind tunnel derived source profiles for herbaceous and wood fuels. Journal of Geophysical Research 102, 36833699. Twomey, S., Warner, J., 1967. The producti on of cloud nuclei by cane fires and the effect on cloud droplet concentration. Journal of Atmospheric Science 24, 704-706. United States Environmental Protecti on Agency (US EPA), 1995. AP-42, fifth ed. Compilation of air pollutant emission fa ctors, vol. 1. O pen Burning (chapter 2.5). Available online at: http://www.epa.gov/ttn/chief/ap42/ch02/final/c02s05.pdf USEPA, 1999a. Compendium method TO -13A: determination of polycyclic aromatic hydrocarbons (PAHs) in ambient air using gas chromatography/mass spectrometry (G CMS). Center for Environmental Research Information, Office of R e search and Development, Cincinnati, OH. USEPA, 1999b, Compendium method TO-11A: determination of formaldehyde in ambient air using adsorbent cartridge followed by high performance liquid chromatography (HPLC) [active sa mpling methodology]. Center for Environmental Research Informa tion, Office of Research and Development, Cincinnati, OH. USEPA, 1999c. Compendium Method TO-15: determinati on of volatile organic compounds (VOCs) in air collected in specially-prepared canisters and analyzed by gas chromatography/mass spectrometry (GC/MS). Center for Environmental Research Informa tion, Office of Research and Development, Cincinnati, OH. USEPA, 2000a. EPA Method 1A: Sample and Velocity Traverses for Stationary Sources with Small Stacks or Ducts. Available online at: http://www.epa.gov/ttn/emc/promgate.html USEPA, 20 00b. EPA Method 18: Measurement of Gaseous Organic Compound Emissions by Gas Chromat ography. Available online at: http://www.epa.gov/ttn/emc/promgate.html USEPA, 20 00c. EPA Method 2: Determinat ion of stack gas velocity and volumetric flow rate (type S pitot tube). Available online at: http://www.epa.gov/ttn/emc/promgate.html USEPA, 2008 a. Other Test Method 27: Determination of PM10 and PM2.5 Emissions From Stationary S ources. Available online at: http://www.epa.gov/ttn/emc/prelim.html

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101 USEPA, 2008 b. Other Te st Method 28: Dry Impinger Method for Determining Condensable Particulate Emissions Fr om Stationary Sources. Available online at: http://www.epa.gov/ttn/emc/prelim.html USEPA, 2010. National Emi ssion Inventory Data and Documentation. Available online at: http://www.epa.gov/ttn/chie f/net/2005inventory.html Ward, D.E. and Hardy, C.C., 1991. Smok e emissions from wildlan d fires. Environment International 17, 117-134. Warner, J.,1968. A reduction in rainfall associated with smoke from sugar-cane firesan inadvertent weather modi fication? Journal of Applied Meteorology 7, 247-251. Wei, W., Wang, S., Chatani, S., Klimont, Z., Cofala, J ., Hao, J., 2008. Emission and speciation of non-methane volatile organic compounds from anthropogenic sources in China. Atmospheric Environment 42, 49764988. Yang, H.H., Tsai, C.H., Chao, M.R., Su, Y.L., Chien, S.M., 2006. Source identification and size distribution of atmospheri c polycyclic aromatic hydrocarbons during rice straw burning period. Atmospheric Environment 40, 1266-1274. Yokelson, R.J., Christian, T.J., Karl, T. G., Guenther, A., 2008. The tropical forest and fire emissions experiment: laboratory fire measurements and synthesis of campaign data. Atmos pheric Chemistry and Physics 8, 35093527. Zamperlini, G.C.M., Silva, M.R.S., Vilegas, V., 2000. Solid-phase extraction of sugarcane soot extract for analysis by gas chromatography with flame ionization and mass spectrometric det ection. Journal of Chromatography A 889, 281-286. Zhang, J. and Smith, K.R., 1999. Emissions of carbonyl compounds from various cookstoves in China. Environmental Science and Technology 33, 23112320. Zheng, M., Cass, G.R., Schauer, J.J. Edgerton, E.S., 2002. Source apportionment of PM2.5 in the southeas tern United States using solventextractable organic compounds as trac ers. Environmental Science and Technology 36, 2361-2371.

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102 BIOGRAPHICAL SKETCH Danielle Lyon Hall was born in Silver Spri ng, Maryland in the summer of 1986. She graduated from Sarasota Hi gh School in 2004 and entered the University of Florid a to study Environmental Engineering. As an undergraduate student she was very involved with her sorority, Kappa Alpha Thet a, which she served as Vice-President of Finance and President in 2006 and 2007, respectively. She was also active in the American Water Works Association (AWWA), serving as treasurer, and in the Air & Waste Management Association (AWMA) Danielle began research as an undergraduate student, participati ng in the University Scholars Program under the direction of Dr. Chang-Yu Wu. She graduated summa cum laude with a B.S. in Environmental Engineering Sc iences in December 2008. Danielle began graduate school in Januar y 2009 to focus on air quality research under the direction of Dr. Chang-Yu Wu. Sh e continued to be active in professional organizations serving as president of AW MA and vice-president of AWWA during the 2008-2009 academic year. She graduated in Ma y 2010 with a M.E. in environmental engineering sciences fr om the University of Florida.