Deliberative, draft document - Do not cite, quote, or distribute Development of VOC Emissions Estimating Methodologies for Animal Feeding Operations Draft Prepared by: U.S. Environmental Protection Agency Office of Air and Radiation Office of Air Quality Planning and Standards 109 T.W. Alexander Drive Research Triangle Park, N.C. 27709 November 2022 This document is a preliminary draft. It has not been formally released by the U. S. Environmental Protection Agency (EPA) and should not at this stage be construed to represent Agency policy. It is being circulated for comments on its technical merit. ------- Deliberative, draft document - Do not cite, quote, or distribute Table of Contents 1 INTRODUCTION 1 2 VOC MEASUREMENT AND DATA COLLECTION 2 2.1 NAEMS Monitoring Protocol 3 2.2 NAEMS Initial VOC Characterization Study 3 2.2.1 Methods 4 2.2.2 Results and Conclusions 5 2.3 NAEMS Monitoring 5 2.3.1 Confinement Sites 5 2.3.2 NAEMS Open Source Site 7 2.3.3 KY Sites 8 2.4 Limitations of NAEMS data 9 2.4.1 NAEMS Confinement Canister Samples 9 2.4.2 NMHC samples 10 3 CALLS FOR INFORMATION 11 4 DATA FROM LITERATURE 11 5 PROPOSED ACTION 11 6 REFERENCES 13 List Of Appendices APPENDIX A:INITIAL VOC CHARACTERIZATION STUDY A-l APPENDIX B: VOC DATA SUMMARY B-l List of Tables Table 1-1. NAEMS sites by process group 2 Table 2-1. Characterization report sites and measurements 4 Table 2-2. VOC samples by process group 6 Table 2-3. Summary of NMHC daily average from KY broiler sites 9 Table B-l. Dairy VOC sample data B-l Table B-2. Poultry VOC sample data B-3 Table B-3. Swine VOC sample data B-5 i ------- Deliberative, draft document - Do not cite, quote, or distribute GLOSSARY / ACRONYMS AFO animal feeding operation bLS backward Lagrangian stochastic CFI call for information ch4 methane EEM emission estimation method EPA Environmental Protection Agency EtOH ethanol FID flame ion detection FRM federal reference method GC-FID gas chromatography with flame ion detection GC-MS gas chromatography-mass spectrometry GSS gas sampling system H2S hydrogen sulfide MeOH methanol mL/min milliliters per minute N H2SO4 normalized sulfuric acid NAEMS National Air Emissions Monitoring Study nh3 ammonia nh4+ ammonium NMHC nonmethane hydrocarbon NMVOC nonmethane volatile organic compounds PAS photoacoustic spectroscopy PIC path integrated concentration PM particulate matter QAPP quality assurance project plan RPM radial plume mapping S-OPS synthetic open-path system THC total hydrocarbon TO toxic organic USDA U.S. Department of Agriculture VFAs volatile fatty acids VOCs volatile organic compounds 11 ------- Deliberative, draft document - Do not cite, quote, or distribute 1 INTRODUCTION With respect to the definitions of criteria air pollutants, the Environmental Protection Agency (EPA) defines volatile organic compounds (VOCs) as any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions (40 CFR 51.100). The vast array of organic chemical compounds that are classified as VOCs evaporate easily at room temperature and can contribute to the odor issues associated with animal feeding operations (AFOs), along with ammonia (NH3) and hydrogen sulfide (H2S). As the science has advanced, the list of VOCs associated with AFOs has grown to more than 500 compounds (Schiffman et al., 2001; Ni 2015). Many of these detected compounds occur at very low concentrations, which makes their measurement difficult and expensive (Janni, 2020). Among the VOCs found at AFOs that contribute to odor are volatile fatty acids (VFAs), alcohols, aldehydes, amides, amines, aromatics, esters, ethers, fixed gases, halogenated hydrocarbons, hydrocarbons, ketones, nitriles, other nitrogen-containing compounds, phenols, sulfur-containing compounds, steroids, and other compounds (Janni, 2020). Since these compounds are closely associated with odor issues, many studies only report VOC concentration in odor units, or correlate concentrations with odor concentrations (Ni, 2015). VOCs are emitted by several sources on AFOs, including animal eructation and exhalation, animal waste in animal pens, flushing lanes, lagoons, silage storage piles and silos, and feed mixtures in feed lanes and bunks (Alanis et al., 2008; Chung et al., 2010). Recent studies at dairies found that VOC concentrations were higher near silage and piles of animal feed (Alanis et al., 2008; Chung et al., 2010; Malkina et al., 2011; Yuan et al., 2017). Yuan et al. (2017) found the percent contribution of the various farm sources (e.g., silage, and animal waste) to VOC emissions could vary by compound and animal type. The complexity of VOC emissions from AFOs make it a topic of continued study. This report outlines the methods used to monitor VOC emissions during the National Air Emissions Monitoring Study (NAEMS), as well as a summary of the data collected, and the limitations of that data. Finally, the report concludes by outlining options for moving forward for initial informal comment by stakeholders. 1 ------- Deliberative, draft document - Do not cite, quote, or distribute 2 VOC MEASUREMENT AND DATA COLLECTION As noted in the process overview report, the 2005 Air Compliance Agreement (Agreement) included a monitoring protocol outlining the pollutants and measurement methodologies to be used in the NAEMS. The monitoring protocol was developed by a broad array of stakeholders that included representatives from the AFO industry; university, United States Department of Agriculture (USDA) and EPA scientists; state and local air quality agencies, and environmental organizations. The monitoring protocol identified a comprehensive list of parameters that were to be monitored to provide a greater understanding and accurate characterization of emissions from AFOs. By monitoring these parameters, the stakeholders believed that the EPA would have the necessary information to develop emission estimation methods (EEMs) for uncontrolled emissions of particulate matter (PM), NH3, H2S, and VOCs from AFOs. The monitoring protocol provided guidance on the number, type and geographical locations of confinement houses and open sources (lagoons and basins) that should be monitored in the NAEMS. The farms that were monitored were selected by the study's Science Advisor, Dr. A1 Heber, and approved by the EPA. Table 1-1 provides a summary of the sites by animal and structure type monitored. The monitoring protocol also identified specific methodologies for measuring emissions from confinement houses and open sources. Confinement houses were to be monitored for PM, NH3, H2S and VOC emissions, while open sources were to be monitored forNEb, EhS and VOC emissions. Table 1-1 . NAEMS sites by process group Animal - Process Structure type Sites Swine - Breeding Gestation Gestation barn IA4B, NC4B, OK4B Swine - Breeding Gestation Farrowing room IA4B, NC4B, OK4B Swine - Breeding Gestation Open source IN4A, NC4A, OK4A Swine - Grow-Finish Finishing barn IN3B, NC3B Swine - Grow-Finish Open source IA3B, NC3A, OK3A Poultry - Broiler House CA1B, KY1B-1, KY1B-2 Poultry - Egg layer Manure belt house IN2B Poultry - Egg layer Manure Shed IN2B Poultry - Egg Layer High rise house CA2B, IN2H, NC2B Dairy Mechanically ventilated barn IN5B, NY5B, WI5B Dairy Milking center IN5B, NY5B, WI5B Dairy Naturally ventilated barn CA5B, WA5B Dairy Open source IN5A, TX5A, WA5A, WI5A 2 ------- Deliberative, draft document - Do not cite, quote, or distribute 2.1 NAEMS Monitoring Protocol The Agreement's monitoring protocol (70 FR 4957, Attachment B) specified that an initial VOC characterization study was to be conducted on a barn for each animal sector participating in the NAEMS. The characterization study was to be conducted on a day during the first month at the first monitored site for an animal sector. Along with building airflow rate, total non-methane hydrocarbons (NMHC) were to be continuously monitored using a dual-channel flame ionization detector (FID) analyzer (EPA Federal Reference Method (FRM) 25A). VOCs were to be sampled with replication at two barns using Silcosteel canisters, and all-glass impingers (modified EPA FRM 26). Each VOC sample was to be evaluated using concurrent gas chromatography-mass spectrometry (GC-MS) and gas chromatography with flame ion detection (GC-FID) for toxic organic (TO) compounds (EPA Method TO-15) and other FID-responding compounds. VOC mass was to be calculated as the sum of individual analytes. The 20 analytes making the greatest contribution to total mass were to be identified during the initial characterization study. A sampling method that captures a significant fraction of the VOC mass was to be chosen for the remainder of the study. The monitoring protocol specified that after the initial VOC characterization study, the selected VOC sampling method would be used to collect quarterly VOC samples at all sites, along with continuous FRM 25 A monitoring at a single site for each animal sector. The FRM 25A measurements were to be corrected from an "as carbon" basis to a total VOC mass basis by multiplying them by the mean molecular weight per carbon atom established by GC-MS evaluations during applicable intervals of time. For open sources, the monitoring protocol specified that samples of the lagoon/basin liquid were to be collected and analyzed for VOC, and the EPA model WATER9 was to be used to estimate emissions based on measured VOC values. The monitoring protocol did not specify either sampling frequency or analytical methodology. 2.2 NAEMS Initial VOC Characterization Study The confinement source quality assurance project plan (QAPP) (Heber et al., 2008) further specified the collections methods of the characterization study to note VOCs were sampled from one site per species at the barn's primary representative exhaust fan using three different methods: sorbent tubes, canisters, and all glass impingers. The methods were elaborated 3 ------- Deliberative, draft document - Do not cite, quote, or distribute on in the "Initial VOC Characterization Study for the NAEMS", which was provided on April 27, 2009 (available in Appendix A) and is summarized in the following sections. 2.2.1 Methods Sorbent tube samples were collected through the gas sampling system exhaust/odor port using a method that allowed the incoming airstream to be split into two roughly equal substreams. Each of these substreams flowed through two pairs of sorbent tubes connected in series. The second tube in the series served as a "breakthrough" tube for the first tube. Additional studies were conducted to determine the optimal length of time for sampling to avoid ice formation in the sample inlet due to excessive water in the tubes. These studies showed that 30 min of sampling time provided an additional margin of safety, while still yielding quantifiable levels of VOCs. Canister sampling was conducted for 24 hours, with 6-liter TO-Can Canisters (Restek Corp, Bellefonte, PA. The flow controllers on the canisters were pre-set in the lab to deliver a flow of approximately 3 milliliters per minute (mL/min). The impinger sampling was conducted using midget (30 mL) all-glass impingers (Ace Glass, Vineland, NJ), with four impingers connected in series. The first two impingers contained 15 mL of 0.1 N H2SO4 for sample collection. The third impinger was a blank to avoid spillover of trapping solution into the fourth impinger, which contained a moisture trap. The impingers collected samples over a two-hour period. The samples were collected at four NAEMS sites, one for each animal species included in NAEMS. Table 2-1 summarizes the sites monitored for the characterization study, and the measurements taken at each. The characterization study did not include any open sources (i.e., lagoons, basins, or corrals). Table 2-2. Characterization report sites and measurements Animal - Process Structure type Sites Measurements Swine - Grow-Finish Finishing barn IN3B 10/23/08 Canisters, sorbent tubes Poultry - Broiler House CA1B 11/18/08 Canisters, sorbent tubes, impingers 12/2/08 Sorbent tubes Poultry - Egg Layer High rise house IN2H 11/5/08 Canisters, sorbent tubes, impingers 11/13/08 Sorbent tubes Dairy Mechanically ventilated barn IN5B 10/15/08 Canisters, sorbent tubes, impingers 10/29/08 Sorbent tubes, impingers 4 ------- Deliberative, draft document - Do not cite, quote, or distribute 2.2.2 Results and Conclusions The impinger sampling detected no significant peaks, other than ammonium (NH4+), and were not considered for further sampling. The primary focus of the characterization study analysis were the canister and sorbent tube samples. The characterization study found the canisters were typically more effective at capturing compounds than sorbent tubes across the sites, especially for the compounds in the 90% mass groups for CA1B and IN5B, and for the single most-dominant compound (isopropyl alcohol) at IN2H. The exception was IN3B, where better performance of tubes relative to canisters was seen. This was attributed to one tube sample containing significantly elevated levels of most analytes relative to the others, thus inflating the average tube-sample yield. The characterization study did note there were several problems encountered with tube sampling, including several samples with sufficient moisture that either could not be analyzed (due to freezing of the GC inlet), or gave extremely distorted chromatograms. The study also saw breakthrough tubes with non-negligible levels of some analytes, which indicates trapping by the primary tube was incomplete. The Science Advisor selected canister sampling over sorbent tubes due to better performance in measuring target compounds and being less challenging to operate. 2.3 NAEMS Monitoring 2.3.1 Confinement Sites The confinement source QAPP (Heber et al., 2008) noted quarterly VOC samples using the selected VOC sampling method from the characterization study were to occur at all sites. Continuous monitoring for total non-methane VOC (NMVOC), and methanol (MeOH)and/or ethanol (EtOH), was planned to be conducted at a minimum of one site per species for the duration of the study. For the continuous measurements, the QAPP (Heber et al., 2008) indicates that concentrations of total NMHC were to be measured using either the INNOVA Model 1412 or a TEI Model 55C. The TEI Model 55C were scheduled to be used at one swine site (IN3B), two dairy sites (CA5B and IN5B), and one layer site (IN2B) as a check on the performance of the INNOVA. 5 ------- Deliberative, draft document - Do not cite, quote, or distribute NAEMS confinement sites followed the QAPP and used the INNOVA analyzed NMHC concentrations by measuring total hydrocarbon (THC) and subtracting EtOH and methane. (CH4) The THC data was questionable, however, due to irreconcilable interferences by water vapor and other gases. Therefore, the VOC-related gas emissions measured by the INNOVA were not included in the final reports or data deliveries to EPA. The Science Advisor also found that continuous NMHC concentrations obtained using the TEI 55C were biased low due to its inability to detect oxygenated VOC. This low bias would have been present in both inlet and exhaust air concentrations. Total nonmethane hydrocarbon (TNMHC) data from IN3B and IN5B were provided in the final reports. This left VOC data obtained using the canisters and analyzed with the GC-MS as the only VOC data provided by the NAEMS effort. The canister sampling frequency specified in the QAPP resulted in only seven sampling events per site. Between January 1, 2009, and October 7, 2010, approximately 7 canisters samples (24-hour sampling period) taken at each NAEMS barn site. Table 22 summarizes the number of valid emissions values. There are between 7 and 39 samples for any structure type monitored under NAEMS. As a comparison, the next small pollutant data set was PM2.5, which also had a limited collection schedule that resulted in a dataset that ranged from 30 (layer manure shed) to 683 (broiler) daily observations for each structure type. However, unlike VOCs, PM2.5 has an advantage in that decisions about parameters affecting PM2.5 emission could be drawn from the more plentiful PM10 data, since PM2.5 is a subset of PM10. The emissions estimates derived from the canister samples are provided in Appendix B. Table 2-3. VOC samples by process group Animal - Process Structure type Number of Samples Swine - Breeding Gestation Gestation barn 30 Swine - Breeding Gestation Farrowing room 12 Swine - Grow-Finish Finishing barn 39 Poultry - Broiler House 13 Poultry - Egg layer Manure belt house 14 Poultry - Egg Layer High rise house 34 Poultry - Egg Layer Pit of high rise house 7 Dairy Mechanically ventilated barn 32 Dairy Milking center 8 Dairy Naturally ventilated barn 15 6 ------- Deliberative, draft document - Do not cite, quote, or distribute The Science Advisor allocated four canisters for each sampling event, which were used to obtain measurements of exhaust air only. There were no inlet air or background concentrations obtained with the canisters, except at CA5B. This means the estimates of VOC emissions provided were gross emissions, where the emissions reported assume zero VOC in the inlet air and thus are a worst-case scenario (i.e., assumes all VOCs monitored are from the source). Inlet sampling at CA5B suggested net emissions were only a small fraction of gross emissions (on average, 22%). It is possible that the particularly low contribution of the CA5B barn might be atypical, as there might have been interference in the measurements from an upwind dairy exercise yard in combination with the additional challenges associated with upwind and downwind sampling at naturally ventilated barns. In light of this, it is hard to conclude all monitored structures would have a similar small contribution to gross emissions. 2.3.2 NAEMS Open Source Site Due to the nature of the open-source emission methodology, the same VOC sampling method could not be used to determine VOC emissions as was used for confinement sources (i.e., 24-hour sampling collection). As noted in Section 2.1, the Agreement's monitoring protocol specified that to estimate VOC emissions from lagoons, samples of the lagoon liquid would be collected and analyzed for VOC, and the WATER9 model would be used to estimate emissions based on measured VOC concentrations, pH, and other factors. However, the open source QAPP (Grant, 2008) proposed a revised method due to difficulties in validating the WATER9 model. The QAPP proposed that emissions of VOCs would be estimated based on synthetic open-path sampling (S-OPS) in conjunction with a gas sampling system (GSS), photoacoustic spectroscopy (PAS), and one to three 3D wind velocity measurements near the surface. The choice of the photoacoustic multi-gas analyzer for the VOC measurements was chosen based on the ability to make continuous accurate measurements of multiple VOCs in combination with NH3. Specifically, the QAPP noted the measurements of CH4, EtOH, MeOH, and residual VOC concentration (as well as NH3 and water vapor concentration and barometric pressure) would be made using PAS, following the Standard Operating Procedure for the Operation of the INNOVA 1412 Photoacoustic multi-gas analyzer (SOP G7). The concentration measurements would be combined with modeling, either inverse dispersion analysis using a backward Lagrangian stochastic method (bLS) or Radial Plume Mapping (RPM), to estimate the VOC emissions. Emissions of CH4, THC, MeOH and EtOH 7 ------- Deliberative, draft document - Do not cite, quote, or distribute were to be calculated using the bLS method or the ratio of VOC measured by PAS from air sampled by the S-OPS to the nearest equivalent NH3 path integrated concertation (PIC) multiplied by RPM calculated emissions of NH3. NMHC emissions were to be calculated by adding the MeOH and EtOH emissions to the THC emissions. Ultimately, no VOC, CH4, THC, MeOH, EtOH, or NMHC values for open-source sites were reported to EPA. Initial efforts with the INNOVA 1412 had interferences by water vapor and other gases, similar to the barn measurement attempts. An email from the Science Advisor did note that an attempt was made to use a TEI Model 55C, in lieu of the INNOVA 1412, at IN5A for the Fall and Winter of 2009-2010. However, no flux estimates of NMHC were made. 2.3.3 KY Sites As described in the process overview report, two additional broiler sites in KY from a Tyson Foods study were included in NAEMS, as the study was developed to be consistent with NAEMS QAPP and provided to EPA for review. Unlike the other NAEMS sites, the QAPP for the KY sites (Moody et al., 2008) specified that THC, CH4, and NMVOC component emissions from the confinement houses would be measured continuously by both an INNOVA 1412 Photoacoustic Multi-gas Monitor and a VIG Industries, Inc. Model-200 total hydrocarbon gas analyzer. According to the QAPP, the INNOVA 1412 was initially intended to be used to measure NH3 and carbon dioxide emissions. However, the VIG Model-200 was unable to achieve the 75% data completeness criteria during the first two months of the study. To address the VOC data completeness issue, the INNOVA 1412 was fitted with additional filters that enabled it to measure CH4 and NMHC in addition to NH3 and carbon dioxide. At the KY sites, an initial characterization study to characterize the speciation of NMHC emitted from the facilities was performed. Stainless steel canisters (Entech Instruments, Inc., Simi Valley, CA) were used to collect the air samples from the two broiler houses (Burns et al., 2009). A GC-MS method was used to speciate the NMHC compounds. A solid sorbent method (TO-17) was used simultaneously to collect the air samples on glass sorbent tubes containing Carbopack X and Carbopack C (2:1 packing volume) custom-made by Supelco, Inc. (Bellafonte, PA) with a GS 301 gas sampler (Gerstel, Inc., Baltimore, MD). Two collection and speciation trials were conducted on April 19, 2006, at Tyson 3-3 (empty house) and Feb 6, 2007, at Tyson 1-5 (with birds in house). The air samples were collected from nine different locations 8 ------- Deliberative, draft document - Do not cite, quote, or distribute throughout the whole house, including each air sampling location. The top 25 compounds were speciated with the TO-15 & TO- 17 methods. During the study, ambient background was not sampled for NMHC (Burns et al., 2009). The researchers assumed that background ambient air consisted of the same NMHC compounds emitted from the houses. They also assumed that the empty house and occupied house had similar chemical profiles for detectable compounds, but the concentrations would change between the empty or occupied house (Burns et al., 2009). As detailed in the QAPP, the confinement house VOC emissions were measured continuously by the INNOVA 1412 and VIG Model-200. However, the data collected by the INNOVA was not reported in the final report because the researchers determined that water vapor caused interference problems with the INNOVA. All the NMHC data presented in the Tyson Foods final report was collected using the VIG Model-200. Despite initial completeness issues with the VIG Model-200, the Tyson study provided NMHC estimates for most of the days on site (Table 2-3). These data are provided in Appendix C. As Section 2.4.2 will detail these continuous NMHC measurements had issues measuring the oxygenated hydrocarbon component of the total VOC. Table 2-4. Summary of NMHC daily average from KY broiler sites site house Days on Site Number of daily averages KY1B-1 H5 394 280 KY1B-2 H3 379 227 2.4 Limitations of NAEMS data The limited quantity of VOC and NMHC samples for the NAEMS sites is problematic for EEM development. In addition, there are quality issues associated with the emission estimates submitted to EPA. The following sections summarize the quality issues with the data collected. 2.4.1 NAEMS Confinement Canister Samples Canisters work well for many non-polar compounds but can have low recoveries of certain compounds including polar compounds such as phenols, indoles, and VFAs (Wang and Austin, 2006). Sorbent tubes can collect a wide range of VOCs including polar VOCs; however, sorbent tubes are more challenging to use due to water sorption in humid environments and artifact formation, as seen during the NAEMS characterization study. The difficulty in collection 9 ------- Deliberative, draft document - Do not cite, quote, or distribute with sorbent tubes contributed to the decision to solely use canisters for VOC collection for the study. A lingering question from NAEMS was whether the canister alone sufficiently captured VOC concentration at the farms. Shortly after the conclusion of NAEMS, USDA Agricultural Research Service (ARS) scientists published a study (Trabue et al., 2010), which examined the type of VOCs emitted from a broiler house using canisters and sorbent tubes simultaneously. Trabue et al. (2010) concluded that neither sorbent tubes nor canisters were only able to capture more than 55% of VOCs present in the house, when considered separately. The implication is that the collection of VOCs by canister during the NAEMS could underpredict total VOC concentration. This coupled with the lack of an inlet measurement, which can contribute a significant portion of VOCs, adds to the uncertainty of the VOC emission estimates generated during NAEMS. 2.4.2 NMHC samples As noted in section 2.3, three sites (CA1B, IN2H and IN3B) analyzed NMHCs using the INNOVA instrument by measuring THC and subtracting EtOH and CH4. Following the NAEMS, the science advisor noted the emissions are inaccurate due to the inaccurate measurement of oxygenated hydrocarbons due to irreconcilable interferences by water vapor and other gases. Similarly, the continuous NMHC measurements from the KY sites measured with the VIG-200 instrument also inaccurately measures the oxygenated hydrocarbon component. The KY measurements were also reported in units of propane, which is different from the NAEMS and add a further challenge to integrate the data. After the NAEMS, a study led by USDA-ARS scientists (Trabue et al., 2013) examined three different commercial NMHC analyzers methods to determine their ability to measure VOCs. Included in the methods studied were the GC/FID model 55C and PA-IR model 1412 (INNOVA model 1412), which were used by NAEMS. The study concluded that NMHC analyzers under-report total VOC concentrations when the compound profiles have significant levels of polar compounds, like at AFOs. The implication is that any NAEMS measurements, including the KY sites, would be an underestimation of NMHC and VOCs for the sites. 10 ------- Deliberative, draft document - Do not cite, quote, or distribute 3 CALLS FOR INFORMATION As part of the NAEMS effort, EPA issued two calls for information (CFI) to collect any additional data that should be considered in developing the NAEMS based EEMs. The first CFI issued in January of 2011, (https://www.regulations.gov/docket/EPA-HQ-OAR-2010-0960) was a broad call for quality-assured emissions and process data relevant to developing EEMs for any pollutant. The second CFI in issued in September of 2019 focused on VOC data for EEM development. Both CFIs yielded several peer reviewed journal articles that contained aggregated VOC emission rates. Under the second CFI, a commentor provided data from the South Lakes Dairy VOC Emission Characterization Report, which was conducted for the Center on Race, Poverty, and the Environment for use in the Association of Irritated Residents v. Fred Schakel Dairy lawsuit. The study was conducted over a two-day period, October 18-19, 2007, with emissions collected via flux chambers, sorbent tubes, and GC-MS. Results from the study were provided as speciated emission rates and factors for various components of the farm. No additional VOC data sets that could be used in an EEM development process like other pollutant collected during NAMES were offered under either of the CFIs. 4 DATA FROM LITERATURE As noted in the introduction, VOC is a complex pollutant as it is the combination of several hundred compounds that can vary depending on the source (animal type and location on the farm) as well as farm conditions, such as meteorological conditions and feed type. Most research on VOC from AFOs is focused on odor or odor mitigation/abatement. As such, results provided in literature are typically in concentration (ppb, etc.) or odor units (OU). Obtaining an accurate estimate of airflow, or ventilation rate, further complicates the ability of researchers to report emissions of VOCs from various farm sources. In a critical review of swine VOC literature, Ni (2012)found only 8% of articles reported VOCs in terms of an emission rate for the farm. This lack of reported VOC emission rate complicates the ability to use information from peer reviewed journal articles to develop emission estimation methods. Additionally, studies often focus on the most odorous, prevalent, or reactive compounds founds at AFOs, instead of total VOC. While not providing a complete picture of VOCs at AFOs, these studies do provide insight into the compounds of key interest to public health and ozone formation. 11 ------- Deliberative, draft document - Do not cite, quote, or distribute Appendix D contains an initial list of information collected from literature to utilize in method development, both total VOC estimates and estimates for individual compounds found on AFOs. 5 PROPOSED ACTION NAEMS is one of the most comprehensive AFO monitoring studies to date. However, the NAEMS VOC data lack the quality and quantity to develop a total VOC EEMs using a similar statistical modeling process utilized for the other pollutants. At this time, EPA is continuing to search literature for data, both total VOC and individual compounds, that can be used to develop an emission estimation method based on subsequent studies that built off the lessons learned in NAEMS. This report summarizes our initial data findings as a progress report for the study. EPA continues to review additional data sources and is working toward providing an estimation method for AFOs to use in evaluating whether they trigger Clean Air Act thresholds. EPA plans on releasing an updated draft with this estimation method in by summer 2023. 12 ------- Deliberative, draft document - Do not cite, quote, or distribute 6 REFERENCES Alanis, P., Sorenson, M., Beene, M., Krauter, C., Shamp, B. and Hasson, A.S., 2008. Measurement of non-enteric emission fluxes of volatile fatty acids from a California dairy by solid phase micro-extraction with gas chromatography/mass spectrometry. Atmospheric Environment, 42(26), pp.6417-6424. Burns, Robert T.; Xin, Hongwei; Gates, Richard S.; Li, Hong; Moody, Lara B.; Overhults, Douglas G.; Earnest, John W.; Hoff, Steven J.; and Trabue, Steven (2009). "Southeastern Broiler Gaseous and Particulate Matter Emissions Monitoring". Agricultural and Biosystems Engineering Technical Reports and White Papers. 7. http://lib.dr.iastate.edu/abe eng reports/7 Chung, M.Y., Beene, M., Ashkan, S., Krauter, C. and Hasson, A.S., 2010. Evaluation of non- enteric sources of non-methane volatile organic compound (NMVOC) emissions from dairies. Atmospheric Environment, 44(6), pp.786-794. Grant, R.H., Grant, R., Heber, A., Nizich, S. and Papp, M., Quality Assurance Project Plan for the National Air Emissions Monitoring Study: Micrometeorological Component. Heber A.J., Ni, J-Q., Ramirez, J.C., Schrock, W., & Elkins, J., 2008. Quality assurance project plan for the National Air Emissions Monitoring Study: Barn Component. Purdue University. Janni, K., 2020. Reflections on odor management for animal feeding operations. Atmosphere, 11(5), p.453. https://doi.org/10.3390/atmosll050453 Malkina, I.L., Kumar, A., Green, P.G. and Mitloehner, F.M., 2011. Identification and quantitation of volatile organic compounds emitted from dairy silages and other feedstuffs. Journal of environmental quality, 40(1), pp.28-36. Moody, L.B., Li, H., Burns, R.T., Xin, H., Gates, R.S., Hoff, S.J. and Overhults, D., 2008. A quality assurance project plan for monitoring gaseous and particulate matter emissions from broiler housing. Am. Soc. Agric. Biol. Eng, pp.1-27. Ni, J. Q., W. P. Robarge, C. Xiao, and A. J. Heber. "Volatile Organic Compounds at Swine Facilities: A Critical Review." Chemosphere 89, no. 7 (Oct 2012): 769-88. https ://doi. org/10.1016/j. chemosphere.2012.04.061. Ni, J.Q., 2015. Research and demonstration to improve air quality for the US animal feeding operations in the 21st century-A critical review. Environmental pollution, 200, pp. 105- 119. Schiffman, S.S., Bennett, J.L. and Raymer, J.H., 2001. Quantification of odors and odorants from swine operations in North Carolina. Agricultural and Forest Meteorology, 108(3), pp.213-240. Trabue, S., Scoggin, K., Li, H., Burns, R., Xin, H. and Hatfield, J., 2010. Speciation of volatile organic compounds from poultry production. Atmospheric environment, 44(29), pp.3538- 3546. Trabue, S., Scoggin, K., McConnell, L.L., Li, H., Turner, A., Burns, R., Xin, H., Gates, R.S., Hasson, A., Ogunjemiyo, S. and Maghirang, R., 2013. Performance of commercial nonmethane hydrocarbon analyzers in monitoring oxygenated volatile organic 13 ------- Deliberative, draft document - Do not cite, quote, or distribute compounds emitted from animal feeding operations. Journal of the Air & Waste Management Association, 63(10), pp.1163-1172. Wang, D.K.W. and Austin, C.C., 2006. Determination of complex mixtures of volatile organic compounds in ambient air: canister methodology. Analytical and bioanalytical chemistry, 386(4), pp. 1099-1120. Yuan, B., Coggon, M.M., Koss, A.R., Warneke, C., Eilerman, S., Peischl, J., Aikin, K.C., Ryerson, T.B. and de Gouw, J.A., 2017. Emissions of volatile organic compounds (VOCs) from concentrated animal feeding operations (CAFOs): chemical compositions and separation of sources. Atmospheric Chemistry and Physics, 17(8), pp.4945-4956. 14 ------- Deliberative, draft document - Do not cite, quote, or distribute Appendix A: Initial VOC Characterization Study A-l ------- Initial VOC Characterization Study for the National Air Emissions Monitoring Study Albert J. Heber, Bill Bogan and Changhe Xiao April 27, 2009 Methodology As specified in the QAPP, VOC's were sampled from one site per species at the barn's primary representative exhaust fan using sorbent tubes (SOP VI), canisters (SOP V2) and all glass impingers (SOP V3). Following several pilot tests of sorbent tubes, the type selected was the 6 mm x 7" TDS tube (Carbotrap 300, Gerstel Inc, Linthicum, MD). Sorbent tube samples were collected through the GSS exhaust/odor port using a sampling box that allowed the incoming airstream to be split into two roughly-equal substreams. Each of these substreams flowed through two pairs of sorbent tubes connected in series such that the second tube served as a "breakthrough" tube for the first tube. Target flow rate was 50 mL/min for each substream. All tubing and fixtures upstream of (and between) the two sorbent tubes were Teflon. Studies were conducted to determine the optimal length of time for sorbent tube sampling to avoid ice blockage of the GC/MS sample inlet due to excessive water in the tubes. These studies showed that sampling from sites IN3B and IN2H should have maximum sampling times of 40-45 min to avoid excessive water, and that 30 min of sampling time provided an additional margin of safety, while still yielding quantifiable levels of VOCs. Simultaneously, based on recommended levels of water that could be introduced without freezing the inlet, psychrometric calculations based on measured sample RH and T (from AirDAC) were used on-site to ensure that excess water would not be trapped. Canister sampling was conducted with 6-L TO-Can Canisters (Restek Corp, Bellefonte, PA), equipped with 1/4" Swagelok SS4H Bellows Valves and 30-psig vacuum pressure gauges. Sampling trains contained Veriflo 423XL flow controllers with 2- to 4-sccm critical orifices and 7-|im in-line stainless steel filters. Flow controllers were pre-set in the lab to deliver approximately 3 mL/min. Canister sampling was conducted for 24 h, and the pressure of the canister was recorded at the beginning and end of the sample period for calculation of total sampled volume. Impinger sampling was conducted using midget (30 mL) all-glass impingers (Ace Glass, Vineland, NJ). For each sample collected, four impingers were connected in series, with the first two each containing 15 mL of 0.1 N H2SO4. The third impinger was a blank to avoid spillover of trapping solution into the fourth impinger, which contained a moisture trap (approximately 20 g of dried silica gel). The inlet of the first impinger was connected to a Teflon filter holder containing a 47-mm PTFE filter membrane (1.0-[j,m pore size), and the outlet of the last impinger was connected first to a 0-5 L/min rotameter, and then to a sampling pump. All connections upstream of the last impinger were Teflon. The sampling pump was set to pull 2 L/min through the impinger train; this flow rate was checked several times during each two-hour sampling period to ensure that it was maintained. 1 ------- Sites sampled, dates, and methods used are as follows: IN2H 11/5 Canisters, sorbent tubes, impingers 11/13 Sorbent tubes IN3B 10/23 Canisters, sorbent tubes IN5B 10/15 Canisters, sorbent tubes, impingers 10/29 Sorbent tubes, impingers CA1B 11/18 Canisters, sorbent tubes, impingers 12/2 Sorbent tubes All the sorbent tube and canister samples were analyzed (SOPs V4 & V6) on an Agilent Model 6890N GC coupled with a Model 5795 MS equipped with a Gerstel TDS-G sample inlet and manual sample introduction. The Electronic Impact mode was utilized. A temperature gradient from 34°C to 250°C was used to separate the compounds. The analytical results were analyzed by ChemStation, and all integrations were manually checked. This method used an external standard compound for instrumental monitoring, instead of an internal standard. This was necessary to avoid losses of low-molecular-weight analytes, which would occur in the purging of any solvent used to introduce the internal standard(s). Emissions calculations for tube samples were conducted. The mass concentration was determined by dividing the mass of a compound detected on the sorbent tube by sampled volume (flow through tube series in mL/min times sampling duration in min). The daily emitted mass was the mass concentration multiplied by barn airflow for the sampling period. The annual emission rate was estimated by multiplying the daily emitted mass by the number of days of sampling (1440/sampling duration in minutes) and by 365. Canister sample analyte concentrations (corrected for dilution necessary to pressurize the canister for sample transfer to the GC) were multiplied by barn airflow for the 24-hour sampling period to yield a daily emission rate, which was then multiplied by 365 to give the annual emission rate. Impinger samples were analyzed (SOP V5) on a Dionex Ion Chromatograph (IC) which consists of a GP50 solvent delivery system, a CD25 conductivity detector, and an autosampler. The IC was equipped with a CS18 cation column and CSRS -II suppressor. The gradient elution ran from 0.5 mM methyl sulfonic acid (MSA) to 30 mM at 0.3 mL/min. The suppressor current was set at 80 mA. The injection volume was 10 |j,L. No compounds other than ammonia were detected in any of the impinger samples. Results Broilers (CA1B) Of the samples collected, three sorbent tube samples from Barn 12 (two on 12/2 and one on 11/18) gave quantifiable results, along with all four canisters 11/18. Emissions rates based on these samples are reported in Table 1. 2 ------- A total of 26 compounds were each detected in at least one exhaust sample. Canister samples yielded greater annual emission rates for 24 of the 26 compounds. The only exceptions were two low-level compounds (dimethyl sulfone and indole) that were undetected in the canisters. By contrast, 17 of the compounds were undetected in any of the sorbent tubes. Fourteen of the 26 compounds contributed to the 90% cumulative mass, led by dimethyl sulfide (21.9%), isopropyl alcohol (17.9%), and acetic acid (15.7%). Isopropyl alcohol was undetected in all sorbent tubes. Dimethyl disulfide, the predominant compound identified at site CA1B, has been reported as a main constituent of broiler emissions detected in previous field studies with canisters (Summers 2005), under laboratory conditions with sorbent tubes (Chang and Chen 2003), and in analysis of headspace above broiler litter in closed chambers (Hobbs et al 1995). Several of the predominant compounds in the CA1B samples were also among the most prevalent in sorbent tube samples collected at several locations in a commercial broiler facility (Trabue et al 2008); these authors generally found acetic acid, butanoic acid and propanoic acid to be the dominant species. Their list of target compounds did not include isopropyl alcohol (which, based on our results, may not have been successfully trapped by tubes anyway) or dimethyl sulfide. Table 1. VOC emission rates calculated for broiler site CA1B from characterization study. # samples with detects Tube/canister Percent of Total Mass Compounds Tubes Canisters Emitted Mass Ratio Analyte Cumulative Sum Dimethyl disulfide 3/3 4/4 0.219 21.9% 21.9% Isopropyl alcohol 0/3 4/4 0.000 17.9% 39.8% Acetic acid 2/3 4/4 1.083 15.7% 55.5% Butanoic acid 0/3 1/4 0.000 5.5% 61.0% Propanoic acid 0/3 1/4 0.000 5.4% 66.4% Methanol 0/3 2/4 0.000 4.8% 71.2% Hexane 2/3 4/4 0.215 3.0% 74.3% Nonanal 3/3 4/4 0.984 3.0% 77.2% Hexanal 1/3 4/4 0.449 2.6% 79.8% Phenol 2/3 4/4 1.523 2.4% 82.2% n-Propanol 1/3 3/4 0.514 2.2% 84.4% Heptanal 0/3 4/4 0.000 2.1% 86.5% Octanal 0/3 3/4 0.000 1.9% 88.4% 4-Methyl phenol 1/3 4/4 0.603 1.7% 90.1% Benzaldehyde 3/3 3/4 1.771 1.60% 91.7% Pentanal 0/3 3/4 0.000 1.5% 93.2% Dimethyl sulfone 2/3 0/4 - 1.5% 94.6% Ethanol 0/3 4/4 0.000 1.0% 95.7% Tridecane 2/3 2/4 4.323 0.94% 96.6% Undecane 2/3 4/4 2.739 0.92% 97.5% Toluene 3/3 4/4 0.428 0.88% 98.4% Benzene 2/3 4/4 0.201 0.61% 99.0% Acetone 0/3 1/4 0.000 0.49% 99.5% Dodecane 0/3 2/4 0.000 0.20% 99.7% Indole 2/3 0/4 - 0.16% 99.9% Pentadecane 0/3 1/4 0.000 0.14% 100.0% 3 ------- Layers (IN2H) Valid results were obtained from a total of five sorbent tubes taken from exhaust air. Three of these samples (two from Barn 6 and one from Barn 7) were collected on 11/5, while the remaining two (both from Barn 7) were collected on 11/13. Valid data were obtained from all four canisters sampled on 11/5. Table 2 below summarizes annual emission rates calculated from these nine samples. Although a total of 27 compounds were detected in at least one tube or canister, isopropyl alcohol alone was responsible for over 85% of the total emitted mass from the IN2H barns. Isopropyl alcohol was successfully trapped by canisters only, and was undetected in any of the sorbent tubes. The combination of isopropyl alcohol, acetic acid and butanoic acid was sufficient to reach 90% of the cumulative mass. In contrast to CA1B, acetic acid, butanoic acid and several minor compounds were trapped better with sorbent tubes than with canisters. These included eight minor compounds that were present in at least one tube sample, but none of the canister samples. However, the failure of tubes to trap isopropyl alcohol clearly rules out their use for this site. An earlier study of organic acids in egg layer houses (Martensson et al 1999) observed that acetic acid was the dominant species, followed by butanoic (butyric) and propanoic (propionic) acids. The relative ratios of these three compounds in IN2H samples (acetic acid was approximately 4 times as abundant as each of the other two compounds) were very similar to those reported by these authors in one of the two houses they studied. Swine (IN3B) All four sorbent tubes and all four canisters from the 10/23 sampling event provided valid emission data (Table 3). Each of 36 individual VOCs were identified in at least one IN3B sample and nine compounds contributed to 90% of the mass. Except for 4-methyl phenol, all nine compounds were organic acids, led by acetic, butanoic and propanoic acids. Unlike any of the other sites, several of the highest-concentration analytes appear to show better trapping by sorbent tubes than by canisters. However, this is mainly due to the presence of one very high-concentration tube sample, which contained approximately eight times more of most analytes than the other three tubes. Had this sample contained analyte levels more commensurate with the others, the tube/canister ratio for most compounds would have been similar to those seen at other sites. An SPME study of indoor air at two Czech swine farms (Ciganek and Neca 2008) reported acetic acid, butanoic acid, />cresol, propanoic acid, pentanoic acid, phenol and hexanal as the primary compounds. Thus, four of the top five compounds from the Czech study match exactly with the top five VOCs identified from IN3B, although />cresol was not detected in the IN3B samples. Phenol and hexanal were also detected from IN3B, albeit not in the list of compounds contributing to the 90% total mass. 4 ------- Table 2. VOC emission rates calculated for layer site IN2H from characterization study. # samples with detects Tube/canister Percent of Total Mass Compounds Tubes Canisters Emitted Mass Ratio Analyte Cumulative Sum Isopropyl alcohol 0/5 4/4 0.000 85.3% 85.3% Acetic acid 4/5 4/4 3.245 4.5% 89.8% Butanoic acid 4/5 3/4 1.938 1.7% 91.5% Acetone 0/5 3/4 0.000 1.6% 93.2% Propanoic acid 3/5 3/4 1.465 1.3% 94.5% Hexanal 5/5 4/4 0.851 0.9% 95.5% Hexane 5/5 4/4 2.466 0.86% 96.3% Nonanal 5/5 3/4 1.380 0.70% 97.0% Heptanal 3/5 4/4 0.321 0.36% 97.4% Benzaldehyde 4/5 4/4 1.653 0.33% 97.7% Dimethyl disulfide 5/5 4/4 1.526 0.28% 98.0% 3-Methyl butanoic acid 2/5 0/4 - 0.27% 98.3% n-Propanol 2/5 4/4 0.854 0.25% 98.5% Octanal 0/5 3/4 0.000 0.23% 98.8% Pentanal 1/5 4/4 0.046 0.17% 98.9% Phenol 1/5 4/4 0.500 0.15% 99.1% 4-Methyl phenol 2/5 4/4 0.483 0.15% 99.2% 2-Methyl propanoic acid 1/5 0/4 - 0.14% 99.4% 2-Methyl butanoic acid 1/5 0/4 - 0.14% 99.5% Dimethyl sulfone 2/5 0/4 - 0.11% 99.6% Ethanol 4/5 4/4 0.289 0.11% 99.7% Undecane 2/5 0/4 - 0.08% 99.8% Toluene 5/5 3/4 2.274 0.06% 99.9% Benzene 4/5 3/4 2.545 0.06% 99.9% Tridecane 1/5 0/4 - 0.03% 100.0% 4-Ethyl phenol 1/5 0/4 - 0.02% 100.0% Propyl butyrate 1/5 0/4 - 0.01% 100.0% As with IN2H, the IN3B organic acid results agreed quite well with a finishing house study by Martensson et al. (1999), who observed that acetic acid was about twice as abundant as either butanoic or propanoic acids, with other acids (valeric, isovaleric, lactic), none of which was detected at IN3B, present at much lower concentrations. Essentially the same results were reported in a study of in vitro incubation of swine manure (Miller and Varel 2003). Our results also closely parallel those of a recent sorbent tube study in a finisher house (Trabue et al 2008), which observed acetic acid, butanoic acid, propanoic acid, 4-methyl phenol and 2-methyl propanoic acid, in that order, to be the most abundant VOCs. Dairy (IN5B) All sorbent tube data from the 10/15 sampling event were invalid. Upon reducing the sampling period from 60 to 30 minutes, all four tubes on 10/29 provided good data. All four of the canister samples from 10/15 were usable. Emissions from site IN5B contained a total of 34 identifiable compounds. Of these, 14 contributed to the 90% mass total. Canisters performed better than tubes for 31 of the 34 5 ------- Table 3. VOC emission rates calculated for swine site IN3B from characterization study. # samples with detects Tube/canister Percent of Total Mass Compounds Tubes Canisters Emitted Mass Ratio Analyte Cumulative Sum Acetic acid 3/4 4/4 4.618 35.9% 35.9% Butanoic acid 4/4 4/4 4.579 18.1% 54.0% Propanoic acid 4/4 4/4 3.631 16.4% 70.4% Pentanoic acid 4/4 4/4 3.117 5.5% 75.8% 3-Methyl butanoic acid 4/4 2/4 4.680 4.0% 79.9% 2-Methyl butanoic acid 4/4 3/4 3.199 3.8% 83.7% 2-Methyl propanoic acid 3/4 4/4 1.350 2.7% 86.4% Hexanoic acid 2/4 0/4 - 2.1% 88.5% 4-Methyl phenol 3/4 4/4 1.022 2.0% 90.5% n-Propanol 3/4 4/4 0.589 1.1% 91.7% 1-Butanol 1/4 3/4 0.245 1.1% 92.8% Phenol 3/4 4/4 0.589 1.0% 93.8% 2-Methyl hexanoic acid 1/4 0/4 - 1.0% 94.8% Ethanol 0/4 3/4 0.000 1.0% 95.7% Methanol 0/4 2/4 0.000 0.79% 96.5% Hexanal 1/4 4/4 0.229 0.35% 96.8% Ethanol 4/4 0/4 - 0.34% 97.2% 2-Butanol 0/4 4/4 0.000 0.30% 97.5% Nonanal 2/4 4/4 0.755 0.29% 97.8% 4-Ethyl phenol 2/4 4/4 1.000 0.27% 98.0% Dimethyl disulfide 1/4 4/4 0.337 0.27% 98.3% Benzaldehyde 3/4 4/4 1.187 0.26% 98.6% Heptanal 0/4 4/4 0.000 0.22% 98.8% Dimethyl sulfone 1/4 4/4 0.515 0.20% 99.0% Isopropyl alcohol 0/4 1/4 0.000 0.13% 99.1% Hexane 1/4 3/4 1.023 0.13% 99.2% n-Propyl acetate 0/4 2/4 0.000 0.12% 99.4% Dodecane 0/4 3/4 0.000 0.11% 99.5% Toluene 4/4 4/4 2.000 0.12% 99.6% Undecane 0/4 4/4 0.000 0.09% 99.7% Tridecane 0/4 4/4 0.000 0.09% 99.8% Benzene 4/4 3/4 0.556 0.08% 99.9% Hexadecane 0/4 2/4 0.000 0.05% 99.9% Indole 2/4 3/4 1.600 0.05% 100.0% Pentadecane 0/4 1/4 0.000 0.03% 100.0% Hexane 0/4 1/4 0.000 0.02% 100.0% compounds, including 23 compounds that were undetected in any of the tubes. The remaining three analytes (ethyl acetate, ethanol and propyl propanoate), each of which was included in the 90% mass cutoff, were trapped equally well by canisters and tubes. Two alcohols (n-propanol and isopropyl alcohol) were the dominant VOCs; ethyl acetate was the only other compound that accounted for >10% of the total emitted mass. Analyses of indoor air from Czech dairies (Ciganek and Neca 2008) showed acetic acid, butanoic acid, propanoic acid, p-cresol and phenol as the predominant compounds. All three of these acids were present in the 90% mass group for the IN5B samples, although they were surpassed by n-propanol, isopropyl alcohol and ethyl acetate. These three compounds either were undetected or were not analyzed for in the Czech study. Martensson et al (1999) identified acetic 6 ------- acid as the primary acid in indoor dairy air samples, although, in their study, it was followed closely by lactic acid, which was undetected in the IN5B samples. Filipy et al (2006) reported ethanol to be the only VOC emitted in significant levels from a WA experimental dairy. Of the five compounds present at higher levels at IN5B, these authors did not detect n-propanol, and do not appear to have targeted isopropyl alcohol, acetic acid, or ethyl acetate. Lastly, several of the most prevalent compounds in the IN5B samples (e.g. acetic acid, propanol, ethanol) were among those measured at the highest levels at a California dairy (Rabaud et al 2003), although several other compounds found at medium-to-high levels (e.g. methyl isobutyrate, butylamine, pyridine, dimethyl sulfoxide, ethyl ether) were not observed at IN5B. Table 4. VOC emission rates calculated for dairy site IN5B from characterization study. # samples with detects Tube/canister Percent of Total Mass Compounds Tubes Canisters Emitted Mass Ratio Analyte Cumulative Sum n-Propanol 4/4 4/4 0.63 31.8% 31.8% Isopropyl alcohol 2/4 4/4 0.09 12.6% 44.4% Ethyl acetate 4/4 4/4 1.13 10.7% 55.1% Acetic acid 2/4 4/4 0.67 8.2% 63.3% Ethanol 4/4 4/4 1.07 6.6% 69.9% n-Propyl acetate 4/4 4/4 0.84 5.8% 75.6% 2-Methyl propanoic acid 0/4 3/4 0.00 4.6% 80.3% Butanoic acid 0/4 2/4 0.00 2.7% 83.0% 2-Methyl hexanoic acid 0/4 1/4 0.00 1.5% 84.5% Propanoic acid 0/4 1/4 0.00 1.5% 85.9% 2-Butanol 2/4 4/4 0.37 1.5% 87.4% Propyl propanonate 4/4 3/4 1.06 1.1% 88.5% 4-Methyl phenol 0/4 4/4 0.00 1.0% 89.5% Pentanal 0/4 4/4 0.00 1.0% 90.5% Hexanal 1/4 4/4 0.08 0.99% 91.5% Heptanal 0/4 4/4 0.00 0.96% 92.4% Octanal 0/4 3/4 0.00 0.85% 93.3% Phenol 0/4 4/4 0.00 0.85% 94.1% 4-Ethyl phenol 0/4 4/4 0.00 0.80% 94.9% Nonanal 0/4 3/4 0.00 0.79% 95.7% Hexane 0/4 4/4 0.00 0.71% 96.4% Benzyl alcohol 0/4 3/4 0.00 0.60% 97.0% Dimethyl disulfide 0/4 4/4 0.00 0.57% 97.6% Benzaldehyde 0/4 4/4 0.00 0.52% 98.1% Propyl butyrate 0/4 2/4 0.00 0.35% 98.5% Toluene 4/4 4/4 0.89 0.27% 98.8% Dodecane 0/4 3/4 0.00 0.22% 99.0% Undecane 0/4 4/4 0.00 0.21% 99.2% Dimethyl sulfone 0/4 1/4 0.00 0.18% 99.4% Propyl hexanoate 0/4 1/4 0.00 0.17% 99.5% 1-Butanol 0/4 1/4 0.00 0.15% 99.7% Propyl pentanoate 0/4 1/4 0.00 0.13% 99.8% n-Butanol 0/4 1/4 0.00 0.11% 99.9% Benzene 4/4 2/4 0.98 0.08% 100.0% 7 ------- Overview of Results Identifications of predominant VOCs, in general, agreed well with existing literature for all four species. Based on the 90% mass cutoffs for each species, the target analyte list for the sampling phase of the NAEMS will consist of 26 compounds (Table 5). Table 5. Target analytes for VOC sampling as determined by the initial characterization study. Compound Present in 90% mass cutoff for: Broilers Layers Swine Dairy Acetic acid + + + + Butanoic acid + + + + 2-Butanol + Dimethyl disulfide + Ethanol + Ethyl acetate + Heptanal + Hexanal + Hexane + Hexanoic acid + Isopropyl alcohol + + + Methanol + 2-Methyl butanoic acid + 3-Methyl butanoic acid + 2-Methyl hexanoic acid + 4-Methyl phenol + + + 2-Methyl propanoic acid + + Nonanal + Octanal + Pentanal + Pentanoic acid + Phenol + Propanoic acid + + + n-Propanol + + n-Propyl acetate + Propyl propanoate + Analyte trapping was usually better with canisters than sorbent tubes, especially for the compounds in the 90% mass groups for CA1B and IN5B, and for the single most-dominant compound (isopropyl alcohol) at IN2H. The apparent better performance of tubes relative to canisters at IN3B was apparently due to one tube sample containing significantly elevated levels of most analytes relative to the others, thus inflating the average tube-sample yield. Several problems were also encountered with tube sampling. Despite the precautions detailed above, a high percentage of the tube samples collected from the CA1B (5/8) and IN2H (3/8) sites contained sufficient moisture that they either could not be analyzed (due to freezing of the GC inlet), or gave extremely distorted chromatograms. The latter is an expected consequence of 8 ------- tubes trapping too much moisture (Trabue et al 2008). Furthermore, breakthrough tubes collected at some sites (e.g. CA1B) did show non-negligible levels of some analytes (data not shown), indicating that trapping by the primary tube was incomplete. Finally, the 30-min tube sampling period introduces considerably more opportunity for sampling bias, as compared with the 24- hour canister sampling, which will represent a full day of site operations, along with all the diurnal variations that might be missed by employing a shorter sampling period. Based on these results, canister sampling will be used exclusively for the ongoing VOC sampling effort. No significant peaks (apart from NH4+) were observed in any of the impinger samples; thus, amine sampling via this method will not be conducted for the remainder of the NAEMS. References Chang, M.H. and T.C. Chen. 2003. Reduction of broiler house malodor by direct feeding of a lactobacilli containing probiotic. International Journal of Poultry Science 2: 313-317. Ciganek, M. and J. Neca. 2008. Chemical characterization of volatile organic compounds on animal farms. VeterinarniMedicina 53:641-651. Filipy, J., B. Rumburg, G. Mount, H. Westberg and B. Lamb. 2006. Identification and quantification of volatile organic compounds from a dairy. Atmospheric Environment 40:1480-1494. Hobbs, P. J., B.F. Pain, T.H. Misselbrook. 1995. Odorous compounds and their emission rates from livestock waste. Proc. Intl. Livestock Odor Conf., ISU, Ames, IA, pp. 11-15. Martensson, L, M. Magnusson, Y. Shen, J.A. Jonsson. 1999. Air concentrations of volatile organic acids in confined animal buildings - determination with ion chromatography. Agriculture, Ecosystems and Environment 75:101-108. Miller, D.N. and V.H. Varel. 2003. Swine manure composition affects the biochemical origins, composition, and accumulation of odorous compounds. J. Animal Science 81:2131-2138. Rabaud, N.E., S.E. Ebeler, L.L. Ashbaugh, R.G. Flocchini. 2003. Characterization and quantification of odorous and non-odorous volatile organic compounds near a commercial dairy in California. Atmospheric Environment 37:933-940. SOP VI. 2009. Sampling of Volatile Organic Compounds (VOCs) in Air Samples through Use of Sorbent Tubes. Standard Operating Procedure, v. 2.0. Purdue Ag Air Quality Lab. SOP V2. 2008. VOC Sampling Using Canisters. Standard Operating Procedure v. 2.0. Purdue Ag Air Quality Lab. SOP V3. 2008. Collection of Amines in Air Samples through Use of Sulfuric Acid-Containing Impingers. Standard Operating Procedure, v. 2.0. Purdue Ag Air Quality Lab. SOP V4. 2008. Thermodesorption and GC/MS Analysis of VOCs Collected on Sorbent Tubes. Standard Operating Procedure, v. 2.0. Purdue Ag Air Quality Lab. SOP V5. 2007. Analysis and Quantitation of Amines by Ion Chromatography. Standard Operating Procedure, v. 1.0. Purdue Ag Air Quality Lab. SOP V6. 2006. Standard Operating Procedure For GC/MS Analysis of VOCs Collected in Sampling Canisters. Standard Operating Procedure, v. 0.0. Purdue Ag Air Quality Lab. Summers, M.D. 2005. Final Report: Quantification of Gaseous Emissions from California Broiler Production Houses, rwww.arb.ca.gov/ag/caf/poulemisrpt.pdfl. Accessed 4/8/09. Trabue, S.L., K.D. Scoggin, H. Li, R. Burns and H. Xin. 2008. Field sampling method for quantifying odorants in humid environments. Env. Sci. and Technology 42:3745-3750. 9 ------- Deliberative, draft document - Do not cite, quote, or distribute A-2 ------- Deliberative, draft document - Do not cite, quote, or distribute Appendix B: VOC Data Summary B-l ------- Deliberative, draft document - Do not cite, quote, or distribute Table B-1. Dairy VOC sample data Animal - Concentration, Airflow, Emission, Site House Process Structure type Date # canisters mg m-3 m3 s"1 kg d"1 IN5B B1 Da ry Mechanically ventilated barn 6/1/2009 l 6.92 259 155 IN5B B1 Da ry Mechanically ventilated barn 6/15/2009 2 2.53 269 58.8 IN5B B1 Da ry Mechanically ventilated barn 8/17/2009 2 3.5 260 78 IN5B B1 Da ry Mechanically ventilated barn 1/19/2010 2 2.95 121 31 IN5B B1 Da ry Mechanically ventilated barn 2/3/2010 2 3.53 121 37 IN5B B1 Da ry Mechanically ventilated barn 2/17/2010 2 2.72 113 26.6 IN5B B1 Da ry Mechanically ventilated barn 3/10/2010 2 1.45 273 34.2 IN5B B2 Da ry Mechanically ventilated barn 6/1/2009 1 5.71 258 127 IN5B B2 Da ry Mechanically ventilated barn 6/15/2009 2 3.89 262 88.1 IN5B B2 Da ry Mechanically ventilated barn 8/17/2009 2 3.76 260 84.2 IN5B B2 Da ry Mechanically ventilated barn 1/19/2010 2 2.35 95.9 19.5 IN5B B2 Da ry Mechanically ventilated barn 2/3/2010 2 3.22 98.3 27.3 IN5B B2 Da ry Mechanically ventilated barn 2/17/2010 2 2.61 99.5 22.4 IN5B B2 Da ry Mechanically ventilated barn 3/10/2010 2 1.03 245 21.8 NY5B B1 Da ry Mechanically ventilated barn 4/24/2009 1 1.87 240 38.7 NY5B B1 Da ry Mechanically ventilated barn 4/27/2009 1 4.44 207 79.5 NY5B B1 Da ry Mechanically ventilated barn 5/27/2009 1 6.24 288 155 NY5B B1 Da ry Mechanically ventilated barn 7/15/2009 2 6.99 305 184 NY5B B1 Da ry Mechanically ventilated barn 9/14/2009 2 5.07 307 134 NY5B B1 Da ry Mechanically ventilated barn 10/26/2009 2 7.68 118 78 NY5B B1 Da ry Mechanically ventilated barn 11/10/2009 2 3.77 113 36.7 NY5B B1 Da ry Mechanically ventilated barn 12/2/2009 1 16.8 22.3 32.2 WI5B B1 Da ry Mechanically ventilated barn 4/6/2009 2 2.39 75.3 15.5 WI5B B1 Da ry Mechanically ventilated barn 6/15/2009 2 1.18 158 16.1 WI5B B1 Da ry Mechanically ventilated barn 7/20/2009 2 0.85 279 20.4 WI5B B1 Da ry Mechanically ventilated barn 8/24/2009 2 0.49 291 12.2 WI5B B1 Da ry Mechanically ventilated barn 9/7/2009 2 0.73 229 14.4 WI5B B2 Da ry Mechanically ventilated barn 4/6/2009 2 2.41 68.8 14.3 WI5B B2 Da ry Mechanically ventilated barn 6/15/2009 2 1.1 210 20.1 WI5B B2 Da ry Mechanically ventilated barn 7/20/2009 2 2.27 329 64.4 WI5B B2 Da ry Mechanically ventilated barn 8/24/2009 2 1.05 343 31.1 WI5B B2 Da ry Mechanically ventilated barn 9/7/2009 2 0.71 288 17.6 WI5B B2 Da ry Mechanically ventilated barn 11/9/2009 2 1.98 N/A N/A B-l ------- Deliberative, draft document - Do not cite, quote, or distribute Animal - Concentration, Airflow, Emission, Site House Process Structure type Date # canisters mg m-3 m3 s"1 kg d"1 WI5B B2 Da ry Mechanically ventilated barn 12/7/2009 2 5.97 N/A N/A NY5B MC Da ry Milking center 4/24/2009 1 1.69 43.5 6.37 NY5B MC Da ry Milking center 4/27/2009 1 0.13 63.2 0.74 NY5B MC Da ry Milking center 5/27/2009 2 2.7 72.2 16.8 NY5B MC Da ry Milking center 7/15/2009 2 2.43 75.1 15.8 NY5B MC Da ry Milking center 9/14/2009 2 1.3 82.7 9.26 NY5B MC Da ry Milking center 10/26/2009 2 1.19 68.3 7.04 NY5B MC Da ry Milking center 11/10/2009 1 0.9 40.8 3.17 NY5B MC Da ry Milking center 12/2/2009 2 5.89 21.8 11.1 CA5B B2 Da ry Naturally ventilated barn 12/18/2009 4 0.292 768 -7.1 CA5B B2 Da ry Naturally ventilated barn 1/8/2010 4 0.924 628 32.3 CA5B B2 Da ry Naturally ventilated barn 1/23/2010 4 1.115 135 9.8 CA5B B2 Da ry Naturally ventilated barn 1/29/2010 4 0.234 1483 5.4 CA5B B2 Da ry Naturally ventilated barn 2/11/2010 4 0.4 2571 10.6 CA5B B2 Da ry Naturally ventilated barn 2/18/2010 4 0.826 1138 -33.4 CA5B B2 Da ry Naturally ventilated barn 2/22/2010 4 0.37 1605 32.2 WA5B B2 Da ry Naturally ventilated barn 5/6/2009 2 0.17 2125 30.9 WA5B B2 Da ry Naturally ventilated barn 6/24/2009 2 0.4 1577 54.1 WA5B B2 Da ry Naturally ventilated barn 9/23/2009 2 0.51 473 20.8 WA5B B2 Da ry Naturally ventilated barn 9/29/2009 2 1.03 1151 102.4 WA5B B4 Da ry Naturally ventilated barn 5/6/2009 1 0.6 1241 64.6 WA5B B4 Da ry Naturally ventilated barn 6/24/2009 2 0.63 1661 89.8 WA5B B4 Da ry Naturally ventilated barn 9/23/2009 2 1.82 359 56.5 WA5B B4 Da ry Naturally ventilated barn 9/29/2009 2 1.83 1256 198.1 B-2 ------- Deliberative, draft document - Do not cite, quote, or distribute Table B-2. Poultry VOC sample data Site House Animal - Process Structure type Date # canisters Concentration, mg m-3 Airflow, m3 s"1 Emission, kg d"1 CA1B H10 Poultry - Broiler House 7/14/2010 2 0.78 58.8 3.94 CA1B H10 Poultry - Broiler House 8/3/2010 2 0.91 4.5 0.35 CA1B H10 Poultry - Broiler House 8/16/2010 2 0.74 18.9 1.21 CA1B H10 Poultry - Broiler House 8/26/2010 2 0.96 30.4 2.53 CA1B H10 Poultry - Broiler House 9/3/2010 2 0.39 56.3 1.89 CA1B H10 Poultry - Broiler House 9/12/2010 2 0.39 51.2 1.72 CA1B H10 Poultry - Broiler House 10/7/2010 2 1.42 5.12 0.63 CA1B H12 Poultry - Broiler House 7/14/2010 2 1.1 59.7 5.7 CA1B H12 Poultry - Broiler House 8/3/2010 2 0.75 4.41 0.29 CA1B H12 Poultry - Broiler House 8/16/2010 2 0.76 18.8 1.24 CA1B H12 Poultry - Broiler House 8/26/2010 2 1.36 29.4 3.45 CA1B H12 Poultry - Broiler House 9/3/2010 2 0.43 55.4 2.06 CA1B H12 Poultry - Broiler House 10/7/2010 2 1.8 4.73 0.73 CA2B H5 Poultry - Egg Layer High rise house 6/9/2009 2 0.55 56.5 2.7 CA2B H5 Poultry - Egg Layer High rise house 6/18/2009 2 1.13 86.2 8.4 CA2B H5 Poultry - Egg Layer High rise house 7/29/2009 2 0.64 78.5 4.34 CA2B H5 Poultry - Egg Layer High rise house 10/2/2009 2 9.58 60 49.7 CA2B H5 Poultry - Egg Layer High rise house 10/12/2009 2 0.38 38.7 1.26 CA2B H5 Poultry - Egg Layer High rise house 10/15/2009 2 0.28 64.4 1.55 CA2B H5 Poultry - Egg Layer High rise house 11/18/2009 2 1 19 1.64 CA2B H6 Poultry - Egg Layer High rise house 6/9/2009 2 0.56 54.5 2.66 CA2B H6 Poultry - Egg Layer High rise house 7/29/2009 2 0.45 72 2.78 CA2B H6 Poultry - Egg Layer High rise house 10/2/2009 2 11.4 55.8 54.9 CA2B H6 Poultry - Egg Layer High rise house 10/12/2009 2 0.41 34.6 1.24 CA2B H6 Poultry - Egg Layer High rise house 10/15/2009 2 0.35 53.9 1.62 CA2B H6 Poultry - Egg Layer High rise house 11/18/2009 2 0.81 33.7 2.35 IN2H H6 Poultry - Egg Layer High rise house 1/9/2009 2 23.5 38.9 78.9 IN2H H6 Poultry - Egg Layer High rise house 3/12/2009 2 1.18 37.3 3.8 IN2H H6 Poultry - Egg Layer High rise house 4/30/2009 2 0.63 55.9 3.05 IN2H H6 Poultry - Egg Layer High rise house 5/9/2009 2 0.6 59.4 3.07 IN2H H6 Poultry - Egg Layer High rise house 5/13/2009 2 1.09 57.3 5.39 IN2H H6 Poultry - Egg Layer High rise house 5/27/2009 2 2.68 58.1 13.5 IN2H H6 Poultry - Egg Layer High rise house 6/23/2009 2 0.52 49.7 2.25 B-3 ------- Deliberative, draft document - Do not cite, quote, or distribute Site House Animal - Process Structure type Date # canisters Concentration, mg m-3 Airflow, m3 s"1 Emission, kg d"1 IN2H H7 Poultry - Egg Layer High rise house 1/9/2009 2 4.67 37.7 15.2 IN2H H7 Poultry - Egg Layer High rise house 3/12/2009 1 1.18 38 3.86 IN2H H7 Poultry - Egg Layer High rise house 4/30/2009 2 0.72 46.2 2.88 IN2H H7 Poultry - Egg Layer High rise house 5/9/2009 2 0.73 46.6 2.96 IN2H H7 Poultry - Egg Layer High rise house 5/13/2009 2 4.91 35.2 14.9 IN2H H7 Poultry - Egg Layer High rise house 5/27/2009 2 0.81 36.7 2.56 IN2H H7 Poultry - Egg Layer High rise house 6/23/2009 2 1.26 19.4 2.11 NC2B H4 Poultry - Egg Layer High rise house 4/12/2009 2 0.45 17.7 0.69 NC2B H4 Poultry - Egg Layer High rise house 4/27/2009 2 0.42 127 4.65 NC2B H4 Poultry - Egg Layer High rise house 5/20/2009 2 0.54 43.4 2.03 NC2B H4 Poultry - Egg Layer High rise house 7/2/2009 2 0.44 178 6.81 NC2B H4 Poultry - Egg Layer High rise house 8/26/2009 2 0.46 220 8.7 NC2B H4 Poultry - Egg Layer High rise house 9/9/2009 2 0.24 130 2.66 NC2B H4 Poultry - Egg Layer High rise house 9/18/2009 2 0.29 80 2.03 NC2B H4 pit Poultry - Egg Layer High rise house 4/12/2009 2 0.54 17.7 0.83 NC2B H4 pit Poultry - Egg Layer High rise house 4/27/2009 2 0.41 128 4.52 NC2B H4 pit Poultry - Egg Layer High rise house 5/20/2009 2 0.62 43.4 2.31 NC2B H4 pit Poultry - Egg Layer High rise house 7/2/2009 2 0.51 178 7.9 NC2B H4 pit Poultry - Egg Layer High rise house 8/26/2009 2 0.29 220 5.51 NC2B H4 pit Poultry - Egg Layer High rise house 9/9/2009 2 0.26 130 2.94 NC2B H4 pit Poultry - Egg Layer High rise house 9/18/2009 2 0.41 80.4 2.83 IN2B B8 Poultry - Egg layer Manure belt house 9/24/2009 2 0.62 90.6 4.88 IN2B B8 Poultry - Egg layer Manure belt house 10/1/2009 2 0.88 74.6 5.7 IN2B B8 Poultry - Egg layer Manure belt house 10/7/2009 2 4.37 73.5 27.7 IN2B B8 Poultry - Egg layer Manure belt house 10/19/2009 2 1.66 67.5 9.7 IN2B B8 Poultry - Egg layer Manure belt house 11/4/2009 2 1.4 67.1 8.1 IN2B B8 Poultry - Egg layer Manure belt house 11/18/2009 2 1.35 66.9 7.8 IN2B B8 Poultry - Egg layer Manure belt house 12/9/2009 2 2.42 57.3 12 IN2B B9 Poultry - Egg layer Manure belt house 9/24/2009 2 0.67 88.1 5.12 IN2B B9 Poultry - Egg layer Manure belt house 10/1/2009 2 0.78 30.5 2.06 IN2B B9 Poultry - Egg layer Manure belt house 10/7/2009 2 6.92 34 20.3 IN2B B9 Poultry - Egg layer Manure belt house 10/19/2009 2 3.14 73.8 20 IN2B B9 Poultry - Egg layer Manure belt house 11/4/2009 2 1.3 14.4 1.62 IN2B B9 Poultry - Egg layer Manure belt house 11/18/2009 2 1.39 29.4 3.53 B-4 ------- Deliberative, draft document - Do not cite, quote, or distribute Animal - Structure Concentration, Airflow, Emission, Site House Process type Date # canisters mg m-3 m3 s"1 kg d"1 IN2B B9 Poultry - Egg layer Manure belt house 12/9/2009 2 0.96 10.5 0.87 Table B-3. Swine VOC sample data Site House Animal - Process Structure type Date # canisters Concentration, mg m-3 Airflow, m3 s"1 Emission, kg d"1 IA4B Far9 Swine - Breeding Gestation Farrowing room 2/19/2009 l 5.67 0.36 0.18 IA4B Far9 Swine - Breeding Gestation Farrowing room 3/5/2009 l 23.6 0.47 0.96 IA4B Far9 Swine - Breeding Gestation Farrowing room 5/27/2010 2 1.89 0.59 0.1 IA4B Far9 Swine - Breeding Gestation Farrowing room 7/1/2010 2 1.16 1.8 0.18 IA4B Far9 Swine - Breeding Gestation Farrowing room 7/29/2010 2 0.52 1.47 0.07 IA4B Far9 Swine - Breeding Gestation Farrowing room 8/6/2010 2 0.67 2.45 0.14 IA4B Far9 Swine - Breeding Gestation Farrowing room 8/12/2009 2 0.43 3.41 0.13 NC4B Far Swine - Breeding Gestation Farrowing room 4/21/2009 1 1.12 2.14 0.21 NC4B Far Swine - Breeding Gestation Farrowing room 5/12/2009 2 0.78 1.86 0.12 NC4B Far Swine - Breeding Gestation Farrowing room 7/4/2009 2 0.23 3.96 0.08 NC4B Far Swine - Breeding Gestation Farrowing room 7/11/2009 2 0.27 4.32 0.1 NC4B Far Swine - Breeding Gestation Farrowing room 8/4/2009 2 1.3 4.89 0.55 IA4B B1 Swine - Breeding Gestation Gestation barn 2/19/2009 1 3.72 10 3.22 IA4B B1 Swine - Breeding Gestation Gestation barn 3/5/2009 1 15 21.3 27.6 IA4B B1 Swine - Breeding Gestation Gestation barn 5/27/2010 2 0.69 27.4 1.64 IA4B B1 Swine - Breeding Gestation Gestation barn 7/1/2010 2 0.29 51.9 1.29 IA4B B1 Swine - Breeding Gestation Gestation barn 8/6/2010 2 0.45 60.1 2.31 IA4B B2 Swine - Breeding Gestation Gestation barn 2/19/2009 1 1.31 9.53 1.08 IA4B B2 Swine - Breeding Gestation Gestation barn 5/27/2010 2 1.46 36 4.56 NC4B B1 Swine - Breeding Gestation Gestation barn 4/21/2009 1 1.19 32.1 3.31 NC4B B1 Swine - Breeding Gestation Gestation barn 5/12/2009 2 0.81 26.5 1.85 NC4B B1 Swine - Breeding Gestation Gestation barn 6/25/2009 2 0.54 84.1 3.9 NC4B B1 Swine - Breeding Gestation Gestation barn 7/4/2009 2 0.19 70.9 1.14 NC4B B1 Swine - Breeding Gestation Gestation barn 8/4/2009 2 1.91 78.4 12.9 NC4B B1 Swine - Breeding Gestation Gestation barn 12/7/2009 2 0.62 7.9 0.42 NC4B B2 Swine - Breeding Gestation Gestation barn 4/21/2009 1 0.68 23.7 1.4 NC4B B2 Swine - Breeding Gestation Gestation barn 5/12/2009 2 1.67 18.8 2.71 B-5 ------- Deliberative, draft document - Do not cite, quote, or distribute Site House Animal - Process Structure type Date # canisters Concentration, mg m-3 Airflow, m3 s"1 Emission, kg d"1 NC4B B2 Swine - Breeding Gestation Gestation barn 6/25/2009 2 0.43 54.3 2.02 NC4B B2 Swine - Breeding Gestation Gestation barn 7/11/2009 2 0.45 46.6 1.83 NC4B B2 Swine - Breeding Gestation Gestation barn 12/7/2009 2 0.62 7.26 0.39 0K4B B1 Swine - Breeding Gestation Gestation barn 4/8/2009 2 0.48 39.2 1.63 0K4B B1 Swine - Breeding Gestation Gestation barn 5/18/2009 2 0.16 44.6 0.62 0K4B B1 Swine - Breeding Gestation Gestation barn 6/9/2009 2 0.45 55.2 2.15 0K4B B1 Swine - Breeding Gestation Gestation barn 7/16/2009 2 0.32 58.5 1.6 0K4B B2 Swine - Breeding Gestation Gestation barn 4/8/2009 2 1.03 35.4 3.14 0K4B B2 Swine - Breeding Gestation Gestation barn 5/18/2009 2 0.77 44.6 2.98 0K4B B2 Swine - Breeding Gestation Gestation barn 6/9/2009 2 0.37 52.9 1.71 0K4B B2 Swine - Breeding Gestation Gestation barn 6/25/2009 2 0.53 69.6 3.17 0K4B B3 Swine - Breeding Gestation Gestation barn 5/18/2009 2 0.3 3.35 0.09 0K4B B3 Swine - Breeding Gestation Gestation barn 6/9/2009 2 0.45 5.14 0.2 0K4B B3 Swine - Breeding Gestation Gestation barn 6/25/2009 2 0.59 6.61 0.34 0K4B B3 Swine - Breeding Gestation Gestation barn 7/16/2009 1 0.42 6.74 0.25 IN3B R5 Swine - Grow-Finish Finishing barn 6/1/2009 1 1 0.66 34.5 IN3B R5 Swine - Grow-Finish Finishing barn 6/8/2009 1 1 0.81 41.7 IN3B R5 Swine - Grow-Finish Finishing barn 6/24/2009 1 1 0.81 48.8 IN3B R5 Swine - Grow-Finish Finishing barn 7/13/2009 1 1 0.29 26.6 IN3B R5 Swine - Grow-Finish Finishing barn 7/22/2009 1 1 1.23 20.9 IN3B R5 Swine - Grow-Finish Finishing barn 7/23/2009 1 1 0.8 26.3 IN3B R6 Swine - Grow-Finish Finishing barn 6/1/2009 1 1 0.95 32.4 IN3B R6 Swine - Grow-Finish Finishing barn 6/8/2009 1 1 4.06 47.7 IN3B R6 Swine - Grow-Finish Finishing barn 6/24/2009 1 1 0.88 48.4 IN3B R6 Swine - Grow-Finish Finishing barn 7/13/2009 1 1 0.79 35.8 IN3B R6 Swine - Grow-Finish Finishing barn 7/22/2009 1 1 1.49 26 IN3B R6 Swine - Grow-Finish Finishing barn 7/23/2009 1 1 0.83 36.2 IN3B R7 Swine - Grow-Finish Finishing barn 6/1/2009 1 1 0.95 32.2 IN3B R7 Swine - Grow-Finish Finishing barn 6/8/2009 1 1 1.03 42.2 IN3B R7 Swine - Grow-Finish Finishing barn 6/24/2009 1 1 0.44 50.5 IN3B R7 Swine - Grow-Finish Finishing barn 7/13/2009 1 1 1.12 42.6 IN3B R7 Swine - Grow-Finish Finishing barn 7/22/2009 1 1 0.62 26.8 IN3B R7 Swine - Grow-Finish Finishing barn 7/23/2009 1 1 0.46 33.8 IN3B R8 Swine - Grow-Finish Finishing barn 6/1/2009 1 1 1.01 32.8 B-6 ------- Deliberative, draft document - Do not cite, quote, or distribute Animal - Structure Concentration, Airflow, Emission, Site House Process type Date # canisters mg m-3 m3 s"1 kg d"1 IN3B R8 Swine - Grow-Finish Finishing barn 6/8/2009 l 1 0.58 41.2 IN3B R8 Swine - Grow-Finish Finishing barn 6/24/2009 l 1 0.52 46.7 IN3B R8 Swine - Grow-Finish Finishing barn 7/13/2009 l 1 1.48 33.6 IN3B R8 Swine - Grow-Finish Finishing barn 7/22/2009 l 1 0.46 32.9 IN3B R8 Swine - Grow-Finish Finishing barn 7/23/2009 l 1 0.81 30.9 NC3B B1 Swine - Grow-Finish Finishing barn 4/24/2009 l 0.37 23.4 0.74 NC3B B1 Swine - Grow-Finish Finishing barn 7/11/2009 2 0.21 22 0.39 NC3B B1 Swine - Grow-Finish Finishing barn 8/3/2009 2 0.49 21.2 0.89 NC3B B1 Swine - Grow-Finish Finishing barn 12/2/2009 2 1.01 7.36 0.64 NC3B B1 Swine - Grow-Finish Finishing barn 12/18/2009 2 0.91 1.43 0.11 NC3B B1 Swine - Grow-Finish Finishing barn 12/26/2009 2 0.78 3.31 0.22 NC3B B2 Swine - Grow-Finish Finishing barn 4/24/2009 1 0.72 29.3 1.81 NC3B B2 Swine - Grow-Finish Finishing barn 7/11/2009 2 0.38 21.9 0.72 NC3B B2 Swine - Grow-Finish Finishing barn 12/11/2009 2 1.06 1.93 0.18 NC3B B2 Swine - Grow-Finish Finishing barn 12/18/2009 2 0.85 2.52 0.19 NC3B B3 Swine - Grow-Finish Finishing barn 4/24/2009 1 0.67 23 1.33 NC3B B3 Swine - Grow-Finish Finishing barn 8/3/2009 2 0.42 21.3 0.78 NC3B B3 Swine - Grow-Finish Finishing barn 12/2/2009 2 1.07 6.81 0.63 NC3B B3 Swine - Grow-Finish Finishing barn 12/11/2009 2 0.7 1.53 0.09 NC3B B3 Swine - Grow-Finish Finishing barn 12/26/2009 2 0.97 3.74 0.31 B-7 ------- Deliberative, draft document - Do not cite, quote, or distribute Appendix C: Tyson NMHC data c-i ------- Deliberative, draft document - Do not cite, quote, or distribute Table C-4. Kentucky NMHC sample data KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 14-Feb-06 25,830 15-Feb-06 25,711 0.80 0.00003 16-Feb-06 25,667 17-Feb-06 25,641 18-Feb-06 25,621 19-Feb-06 25,605 20-Feb-06 25,585 25,515 0.67 0.00003 21-Feb-06 25,572 25,486 1.36 0.00005 22-Feb-06 25,551 25,460 1.39 0.00005 23-Feb-06 25,536 25,424 24-Feb-06 25,525 1.30 0.00005 25,342 25-Feb-06 25,510 1.49 0.00006 25,286 26-Feb-06 25,493 1.77 0.00007 25,265 27-Feb-06 25,475 1.97 0.00008 25,264 28-Feb-06 25,460 1.47 0.00006 25,239 l-Mar-06 25,449 1.23 0.00005 25,222 2-Mar-06 25,440 1.35 0.00005 25,202 3-Mar-06 25,430 1.89 0.00007 25,180 2.30 0.00009 4-Mar-06 25,419 1.74 0.00007 25,157 1.47 0.00006 5-Mar-06 25,400 1.43 0.00006 25,141 6-Mar-06 25,397 1.11 0.00004 25,120 7-Mar-06 25,389 1.62 0.00006 25,100 1.72 0.00007 8-Mar-06 25,382 1.73 0.00007 25,072 1.09 0.00004 9-Mar-06 25,376 1.21 0.00005 25,058 10-Mar-06 25,371 1.24 0.00005 25,044 ll-Mar-06 25,365 25,037 12-Mar-06 25,358 25,029 13-Mar-06 25,350 25,023 14-Mar-06 25,346 25,012 15-Mar-06 25,338 1.62 0.00006 25,008 1.17 0.00005 16-Mar-06 25,332 2.46 0.00010 24,991 1.11 0.00004 17-Mar-06 25,322 1.84 0.00007 24,980 1.53 0.00006 18-Mar-06 25,315 1.77 0.00007 24,963 2.11 0.00008 19-Mar-06 25,307 1.36 0.00005 24,953 1.49 0.00006 20-Mar-06 25,302 1.89 0.00007 24,941 21-Mar-06 25,288 1.68 0.00007 24,928 22-Mar-06 25,282 2.07 0.00008 24,907 1.26 0.00005 23-Mar-06 25,275 2.56 0.00010 24,891 1.75 0.00007 24-Mar-06 25,267 2.27 0.00009 24,880 1.68 0.00007 25-Mar-06 25,257 2.40 0.00010 24,872 1.52 0.00006 26-Mar-06 25,246 1.80 0.00007 24,856 1.66 0.00007 27-Mar-06 25,237 1.94 0.00008 24,825 1.06 0.00004 28-Mar-06 25,222 24,780 1.17 0.00005 29-Mar-06 25,212 24,759 2.45 0.00010 30-Mar-06 25,177 24,728 1.85 0.00008 31-Mar-06 25,158 24,709 1.73 0.00007 C-2 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd l-Apr-06 25,158 24,698 1.42 0.00006 2-Apr-06 25,158 24,677 3-Apr-06 25,158 24,643 4-Apr-06 25,158 24,619 3.14 0.00013 5-Apr-06 24,598 6-Apr-06 24,579 7-Apr-06 24,486 8-Apr-06 24,284 9-Apr-06 24,167 0.74 0.00003 10-Apr-06 24,167 0.77 0.00003 ll-Apr-06 0.78 12-Apr-06 1.08 13-Apr-06 0.83 14-Apr-06 0.13 0.64 15-Apr-06 0.00 0.43 16-Apr-06 0.30 0.03 17-Apr-06 0.18 0.05 18-Apr-06 19-Apr-06 20-Apr-06 0.88 21-Apr-06 22995 0.29 0.00001 22-Apr-06 22840 0.31 0.00001 23-Apr-06 22748 0.37 0.00002 24-Apr-06 22690 0.41 0.00002 25-Apr-06 22625 0.46 0.00002 26-Apr-06 22578 27-Apr-06 22517 0.03 28-Apr-06 22462 1.01 0.00004 0.06 29-Apr-06 22437 0.93 0.00004 0.01 30-Apr-06 22418 1.07 0.00005 0.00 l-May-06 22408 1.19 0.00005 0.00 2-May-06 22394 1.25 0.00006 0.00 3-May-06 22382 2.56 0.00011 0.00 4-May-06 22365 2.55 0.00011 0.00 5-May-06 22347 1.89 0.00008 0.00 6-May-06 22333 2.10 0.00009 0.00 7-May-06 22321 2.10 0.00009 0.00 8-May-06 22312 1.93 0.00009 0.03 9-May-06 22290 1.46 0.00007 0.00 10-May-06 22278 0.78 0.00004 0.00 ll-May-06 22256 0.79 0.00004 0.00 12-May-06 22245 0.92 0.00004 0.00 13-May-06 22235 0.94 0.00004 0.00 14-May-06 22227 0.88 0.00004 0.00 15-May-06 22220 0.72 0.00003 0.11 16-May-06 22214 0.60 0.00003 0.04 17-May-06 22210 0.82 0.00004 0.06 C-3 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 18-May-06 22203 0.00 19-May-06 22193 0.80 0.00004 0.00 20-May-06 22178 0.84 0.00004 0.00 21-May-06 22168 0.75 0.00003 0.11 22-May-06 22160 0.88 0.00004 24,450 0.50 0.00002 23-May-06 22147 24,439 0.45 0.00002 24-May-06 22136 0.88 0.00004 24,421 0.46 0.00002 25-May-06 22126 1.62 0.00007 24,394 0.90 0.00004 26-May-06 22086 1.31 0.00006 24,377 0.73 0.00003 27-May-06 22074 2.83 0.00013 24,356 0.78 0.00003 28-May-06 22064 2.74 0.00012 24,338 1.08 0.00004 29-May-06 22051 2.87 0.00013 24,311 0.76 0.00003 30-May-06 22021 1.95 0.00009 24,292 0.92 0.00004 31-May-06 22001 24,274 1.04 0.00004 l-Jun-06 21983 24,246 1.10 0.00005 2-Jun-06 21964 24,229 0.64 0.00003 3-Jun-06 21889 1.89 0.00009 24,214 0.75 0.00003 4-Jun-06 21854 24,199 0.65 0.00003 5-Jun-06 21788 24,179 0.79 0.00003 6-Jun-06 21762 2.82 0.00013 24,168 0.79 0.00003 7-Jun-06 21708 4.05 0.00019 24,153 0.81 0.00003 8-Jun-06 21634 3.86 0.00018 24,142 0.98 0.00004 9-Jun-06 21634 3.00 0.00014 24,133 0.71 0.00003 10-Jun-06 3.60 24,123 0.88 0.00004 ll-Jun-06 2.18 24,115 0.64 0.00003 12-Jun-06 1.30 24,108 13-Jun-06 1.43 24,102 1.01 0.00004 14-Jun-06 24,092 1.45 0.00006 15-Jun-06 0.84 24,083 1.33 0.00006 16-Jun-06 1.81 24,075 1.12 0.00005 17-Jun-06 0.85 24,067 1.40 0.00006 18-Jun-06 0.14 24,061 1.07 0.00004 19-Jun-06 0.38 24,059 20-Jun-06 0.63 24,056 21-Jun-06 1.04 24,052 2.20 0.00009 22-Jun-06 24465 0.75 0.00003 24,049 0.72 0.00003 23-Jun-06 24396 0.41 0.00002 24,041 0.83 0.00003 24-Jun-06 24355 0.68 0.00003 24,031 25-Jun-06 24324 0.45 0.00002 24,024 26-Jun-06 24291 24,012 27-Jun-06 24262 24,004 28-Jun-06 24240 23,991 29-Jun-06 24211 23,981 30-Jun-06 24199 23,968 1.12 0.00005 l-Jul-06 24189 23,948 1.96 0.00008 2-Jul-06 24182 23,940 2.99 0.00013 3-Jul-06 24168 23,919 C-4 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 4-Jul-06 24156 23,902 5-Jul-06 24151 23,873 6-Jul-06 24147 23,848 7-Jul-06 24142 23,818 8-Jul-06 24135 23,768 9-Jul-06 24129 23,718 10-Jul-06 24123 23,718 ll-Jul-06 24108 23,718 12-Jul-06 24100 13-Jul-06 24086 14-Jul-06 24066 15-Jul-06 24060 16-Jul-06 24053 17-Jul-06 24034 18-Jul-06 24025 19-Jul-06 24019 20-Jul-06 24014 21-Jul-06 24006 22-Jul-06 24000 0.83 0.00003 23-Jul-06 23993 1.22 0.00005 0.00 24-Jul-06 23982 1.07 0.00004 25-Jul-06 23972 1.29 0.00005 26-Jul-06 23965 1.72 0.00007 27-Jul-06 23941 1.74 0.00007 28-Jul-06 23933 24,380 29-Jul-06 23924 24,341 30-Jul-06 23918 24,309 31-Jul-06 23896 24,281 0.55 0.00002 l-Aug-06 23885 24,264 2-Aug-06 23870 24,231 3-Aug-06 23861 24,209 4-Aug-06 23843 4.28 0.00018 24,198 0.41 0.00002 5-Aug-06 23808 3.28 0.00014 24,188 0.63 0.00003 6-Aug-06 23795 3.99 0.00017 24,174 0.40 0.00002 7-Aug-06 23752 4.82 0.00020 24,163 0.63 0.00003 8-Aug-06 23752 4.78 0.00020 24,150 0.68 0.00003 9-Aug-06 23752 4.09 0.00017 24,139 0.62 0.00003 10-Aug-06 23752 4.35 0.00018 24,130 ll-Aug-06 2.72 24,123 12-Aug-06 24,111 13-Aug-06 24,103 14-Aug-06 24,098 15-Aug-06 0.77 24,090 0.79 0.00003 16-Aug-06 0.00 24,085 0.84 0.00003 17-Aug-06 0.26 24,078 18-Aug-06 1.26 24,072 19-Aug-06 2.31 24,067 C-5 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 20-Aug-06 1.74 24,064 21-Aug-06 1.75 24,062 22-Aug-06 24,058 23-Aug-06 24,052 1.16 0.00005 24-Aug-06 1.04 24,047 0.65 0.00003 25-Aug-06 0.23 24,044 0.97 0.00004 26-Aug-06 0.03 24,040 0.99 0.00004 27-Aug-06 0.01 24,038 0.56 0.00002 28-Aug-06 0.03 24,037 0.68 0.00003 29-Aug-06 0.31 24,034 1.13 0.00005 30-Aug-06 0.12 24,029 1.16 0.00005 31-Aug-06 0.15 24,021 1.23 0.00005 l-Sep-06 24,018 1.74 0.00007 2-Sep-06 24,011 1.35 0.00006 3-Sep-06 23,996 1.38 0.00006 4-Sep-06 0.06 23,980 1.73 0.00007 5-Sep-06 25695 0.19 0.00001 23,976 2.05 0.00009 6-Sep-06 25680 0.24 0.00001 23,968 2.15 0.00009 7-Sep-06 25665 0.35 0.00001 23,948 2.03 0.00008 8-Sep-06 25646 0.24 0.00001 23,937 9-Sep-06 25635 0.59 0.00002 23,927 10-Sep-06 25622 0.58 0.00002 23,914 ll-Sep-06 25610 0.52 0.00002 23,892 12-Sep-06 25596 0.67 0.00003 23,875 13-Sep-06 25587 0.70 0.00003 23,863 14-Sep-06 25578 1.23 0.00005 23,848 2.76 0.00012 15-Sep-06 25561 1.63 0.00006 23,833 3.24 0.00014 16-Sep-06 25550 1.13 0.00004 23,809 3.13 0.00013 17-Sep-06 25540 0.98 0.00004 23,809 2.63 0.00011 18-Sep-06 25523 0.76 0.00003 23,809 0.00 0.00000 19-Sep-06 25509 0.84 0.00003 23,809 2.30 0.00010 20-Sep-06 25499 0.82 0.00003 0.38 21-Sep-06 25486 0.97 0.00004 22-Sep-06 25472 0.76 0.00003 23-Sep-06 25449 0.99 0.00004 24-Sep-06 25433 1.05 0.00004 1.37 25-Sep-06 25417 1.02 0.00004 0.64 26-Sep-06 25389 1.10 0.00004 1.03 27-Sep-06 25374 1.56 0.00006 0.78 28-Sep-06 25356 1.12 0.00004 0.02 29-Sep-06 25347 1.15 0.00005 0.12 30-Sep-06 25335 1.16 0.00005 0.21 l-Oct-06 25325 1.73 0.00007 0.00 2-Oct-06 25312 1.18 0.00005 0.00 3-Oct-06 25300 0.95 0.00004 0.06 4-Oct-06 25286 1.24 0.00005 0.22 5-Oct-06 25267 0.86 0.00003 25,778 C-6 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 6-Oct-06 25257 1.07 0.00004 25,734 0.65 0.00003 7-Oct-06 25243 1.14 0.00005 25,704 0.63 0.00002 8-Oct-06 25173 1.06 0.00004 25,659 0.67 0.00003 9-Oct-06 25121 1.10 0.00004 25,631 0.47 0.00002 10-0ct-06 25100 1.08 0.00004 25,601 0.50 0.00002 ll-Oct-06 25027 25,576 12-Oct-06 24994 25,552 1.18 0.00005 13-Oct-06 24824 1.79 0.00007 25,538 1.24 0.00005 14-Oct-06 24782 1.47 0.00006 25,528 1.04 0.00004 15-Oct-06 24485 1.35 0.00006 25,522 1.32 0.00005 16-Oct-06 24402 1.95 0.00008 25,487 0.80 0.00003 17-Oct-06 24340 2.54 0.00010 25,410 0.98 0.00004 18-Oct-06 24296 2.34 0.00010 25,405 1.17 0.00005 19-Oct-06 24278 2.11 0.00009 25,398 1.40 0.00006 20-0ct-06 24231 3.05 0.00013 25,393 1.73 0.00007 21-Oct-06 24183 3.27 0.00014 25,386 0.93 0.00004 22-Oct-06 24165 3.21 0.00013 25,381 1.43 0.00006 23-Oct-06 24046 2.95 0.00012 25,376 0.95 0.00004 24-Oct-06 24046 3.22 0.00013 25,367 1.92 0.00008 25-Oct-06 24046 4.14 0.00017 25,364 1.41 0.00006 26-Oct-06 1.97 25,360 1.02 0.00004 27-Oct-06 0.78 25,357 1.00 0.00004 28-Oct-06 0.85 25,353 0.99 0.00004 29-Oct-06 0.40 25,347 1.03 0.00004 30-0ct-06 0.00 25,334 0.94 0.00004 31-Oct-06 0.00 25,328 1.30 0.00005 l-Nov-06 0.04 25,326 1.49 0.00006 2-Nov-06 25,323 1.57 0.00006 3-Nov-06 0.59 25,319 1.76 0.00007 4-Nov-06 0.08 25,316 1.96 0.00008 5-Nov-06 0.00 25,314 1.86 0.00007 6-Nov-06 0.62 25,311 1.58 0.00006 7-Nov-06 25,307 1.90 0.00008 8-Nov-06 0.28 25,300 2.08 0.00008 9-Nov-06 0.44 25,294 2.29 0.00009 10-Nov-06 1.04 25,289 ll-Nov-06 0.30 25,286 12-Nov-06 0.22 25,279 13-Nov-06 0.01 25,262 14-Nov-06 0.05 25,256 15-Nov-06 0.02 25,246 16-Nov-06 0.55 25,229 17-Nov-06 25080 0.46 0.00002 25,213 18-Nov-06 25000 25,199 19-Nov-06 24396 25,176 20-Nov-06 23358 0.94 0.00004 25,148 21-Nov-06 22248 1.35 0.00006 25,113 C-7 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 22-Nov-06 21048 1.19 0.00006 25,113 23-Nov-06 20276 1.13 0.00006 25,113 24-Nov-06 19626 0.98 0.00005 25,113 25-Nov-06 19201 0.89 0.00005 25,113 26-Nov-06 19051 0.89 0.00005 25,113 27-Nov-06 18328 0.64 0.00003 25,113 28-Nov-06 18039 0.68 0.00004 29-Nov-06 17790 0.67 0.00004 30-Nov-06 17305 0.38 0.00002 l-Dec-06 17191 0.00 2-Dec-06 17003 3-Dec-06 16913 0.00 4-Dec-06 16528 0.96 5-Dec-06 16420 0.85 0.00005 0.74 6-Dec-06 16301 1.29 0.00008 0.29 7-Dec-06 16231 2.08 0.00013 0.09 8-Dec-06 16171 2.50 0.00015 0.07 9-Dec-06 16127 2.20 0.00014 0.00 10-Dec-06 16102 2.10 0.00013 0.07 ll-Dec-06 16064 2.12 0.00013 0.27 12-Dec-06 16022 13-Dec-06 15966 14-Dec-06 15932 2.37 0.00015 24,970 15-Dec-06 15862 2.63 0.00017 24,917 16-Dec-06 15820 2.52 0.00016 24,872 0.79 0.00003 17-Dec-06 15800 1.96 0.00012 24,806 18-Dec-06 15774 2.50 0.00016 24,762 19-Dec-06 15718 3.19 0.00020 24,730 20-Dec-06 15690 4.17 0.00027 24,706 21-Dec-06 15649 1.34 0.00009 24,690 22-Dec-06 15624 1.70 0.00011 24,676 23-Dec-06 15556 2.67 0.00017 24,664 0.51 0.00002 24-Dec-06 15466 3.12 0.00020 24,652 0.46 0.00002 25-Dec-06 15379 2.75 0.00018 24,634 0.42 0.00002 26-Dec-06 15149 3.41 0.00022 24,623 0.40 0.00002 27-Dec-06 14919 2.13 0.00014 24,612 28-Dec-06 14675 1.87 0.00013 24,603 29-Dec-06 14571 2.14 0.00015 24,594 30-Dec-06 14316 1.39 0.00010 24,591 31-Dec-06 14248 1.48 0.00010 24,586 l-Jan-07 14061 2.52 0.00018 24,583 2-Jan-07 13946 2.19 0.00016 24,577 3-Jan-07 13876 2.12 0.00015 24,570 0.80 0.00003 4-Jan-07 13876 1.69 0.00012 24,562 0.68 0.00003 5-Jan-07 13876 1.65 0.00012 24,559 6-Jan-07 13876 1.45 0.00010 24,551 0.90 0.00004 7-Jan-07 13876 1.48 0.00011 24,541 0.98 0.00004 C-8 ------- Deliberative, draft document - Do not cite, quote, or distribute KY1B-1 KY1B-2 Date Bird# NMHC,lbs NMHC, Ibs/hd Bird# NMHC, lbs NMHC, Ibs/hd 8-Jan-07 13876 1.73 0.00012 24,538 1.14 0.00005 9-Jan-07 13876 1.52 0.00011 24,532 1.18 0.00005 10-Jan-07 0.23 24,519 1.26 0.00005 ll-Jan-07 0.04 24,506 1.30 0.00005 12-Jan-07 1.68 24,499 1.47 0.00006 13-Jan-07 0.42 24,490 1.19 0.00005 14-Jan-07 0.20 24,482 1.25 0.00005 15-Jan-07 0.55 24,464 1.23 0.00005 16-Jan-07 1.36 24,452 1.44 0.00006 17-Jan-07 1.00 24,430 1.33 0.00005 18-Jan-07 0.19 24,401 1.46 0.00006 19-Jan-07 0.26 24,381 1.49 0.00006 20-Jan-07 0.00 24,362 1.88 0.00008 21-Jan-07 24,344 2.27 0.00009 22-Jan-07 26600 24,320 1.96 0.00008 23-Jan-07 26500 24,299 2.19 0.00009 24-Jan-07 26465 24,275 2.92 0.00012 25-Jan-07 26427 24,241 2.68 0.00011 26-Jan-07 26404 24,206 2.90 0.00012 27-Jan-07 26374 24,171 2.79 0.00012 28-Jan-07 26323 24,133 3.10 0.00013 29-Jan-07 26307 24,103 30-Jan-07 26290 24,050 31-Jan-07 26272 24,050 l-Feb-07 26260 24,050 3.84 0.00016 2-Feb-07 26244 24,050 1.73 0.00007 3-Feb-07 26234 0.26 4-Feb-07 26228 0.73 5-Feb-07 26220 0.49 6-Feb-07 26199 7-Feb-07 26167 0.06 8-Feb-07 26142 0.05 9-Feb-07 26055 2.72 0.00010 10-Feb-07 26030 1.81 0.00007 ll-Feb-07 25981 1.12 0.00004 12-Feb-07 25884 0.87 0.00003 26,013 0.22 0.00001 13-Feb-07 25861 1.23 0.00005 25,992 0.24 0.00001 14-Feb-07 25846 1.72 0.00007 25,958 0.23 0.00001 15-Feb-07 25808 2.64 0.00010 25,926 0.32 0.00001 16-Feb-07 25790 2.75 0.00011 25,887 0.35 0.00001 17-Feb-07 25784 1.85 0.00007 25,852 0.41 0.00002 18-Feb-07 25764 2.37 0.00009 25,821 0.46 0.00002 19-Feb-07 25751 1.80 0.00007 25,802 0.47 0.00002 20-Feb-07 25720 2.12 0.00008 25,772 0.53 0.00002 21-Feb-07 25701 1.75 0.00007 25,748 0.83 0.00003 22-Feb-07 25690 2.05 0.00008 25,730 23-Feb-07 25677 2.11 0.00008 25,714 C-9 ------- Deliberative, draft document - Do not cite, quote, or distribute Date Bird# KY1B- NMHC,lbs 1 NMHC, Ibs/hd Bird# kyib-; NMHC, lbs NMHC, Ibs/hd 24-Feb-07 25660 1.64 0.00006 25,697 25-Feb-07 25634 0.96 0.00004 25,681 26-Feb-07 25609 1.92 0.00008 25,672 27-Feb-07 25580 4.47 0.00017 25,664 28-Feb-07 25497 4.62 0.00018 25,656 l-Mar-07 25345 4.02 0.00016 25,648 2-Mar-07 25269 3.86 0.00015 25,648 3-Mar-07 25159 4.04 0.00016 25,648 4-Mar-07 25052 3.97 0.00016 25,648 5-Mar-07 24948 3.36 0.00013 25,648 6-Mar-07 24670 4.76 0.00019 7-Mar-07 24655 4.44 0.00018 8-Mar-07 24633 4.65 0.00019 9-Mar-07 24604 10-Mar-07 24575 5.24 0.00021 ll-Mar-07 24546 4.49 0.00018 12-Mar-07 24546 4.96 0.00020 13-Mar-07 24546 4.84 0.00020 14-Mar-07 24546 2.68 0.00011 C-10 ------- Deliberative, draft document - Do not cite, quote, or distribute Appendix D: Emission Factors from Literature D-l ------- Deliberative, draft document - Do not cite, quote, or distribute Table C-51. Total VOC Emissions Factors from literature Farm Type Structure Type Emission Factor Unit of Emission Factor Reference Dairy, (> 1,000 milk cows) Enteric Emissions from Cows 4.10 Ib/hd-yr Sheraz and Norman, 2012 Dairy, (> 1,000 milk cows) Milking Parlor(s) 0.03 Ib/hd-yr Sheraz and Norman, 2012 Dairy, (> 1,000 milk cows) Freestall Barns 1.80 Ib/hd-yr Sheraz and Norman, 2012 Dairy, (> 1,000 milk cows) Corrals/Pens 6.60 Ib/hd-yr Sheraz and Norman, 2012 Dairy, (> 1,000 milk cows) Liquid Manure Handling (lagoons, storage ponds, basins) 1.30 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (> 1,000 milk cows) Liquid manure land application 1.40 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (> 1,000 milk cows) Solid manure land application 0.33 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (> 1,000 milk cows) Separated solids piles 0.06 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (> 1,000 milk cows) Solid manure storage 0.15 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Enteric Emissions from Cows 4.30 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Milking Parlor(s) 0.04 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Freestall Barns 1.90 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Corrals/Pens 10.00 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Liquid Manure Handling (lagoons, storage ponds, basins) 1.50 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Liquid manure land application 1.60 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Solid manure land application 0.39 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Separated solids piles 0.06 Ib/hd-yr Sheraz and Norman, 2012 Da ry, (< 1,000 milk cows) Solid manure storage 0.16 Ib/hd-yr Sheraz and Norman, 2012 Da ry Milking cows 12.800 Ib/hd-yr AQMD, 2016 Da ry Dry Cows 8.700 Ib/hd-yr AQMD, 2016 Da ry Heifer (4-24 months) 6.100 Ib/hd-yr AQMD, 2016 Da ry Heifer (4-24 months), with flush lanes that are flushed with water to a holding pond 4.700 Ib/hd-yr AQMD, 2016 Dairy Calf (under 3 months) 4.500 Ib/hd-yr AQMD, 2016 D-l ------- Deliberative, draft document - Do not cite, quote, or distribute Emission Unit of Farm Type Structure Type Factor Emission Factor Reference Layers Manure from Laying hens and associated birds 0.026 Ib/hd-yr AQMD, 2016 Broilers Manure from Broiler chickens and associated birds 0.026 Ib/hd-yr AQMD, 2016 Dairy Lagoon 4.500 Ib/yr-AU EPA, 2001 Swine Lagoon 2.400 Ib/yr-AU EPA, 2001 Layer Lagoon 4.000 Ib/yr-AU EPA, 2001 Swine Finishing pig 30.300 mg d-1 kg hd Feilberg, et al., 2010 Swine Finishing pig, shallow pit 4.99 mg d-1 kg hd Heber et al, 2004 Dairy Stable 11.10 kg/yr/hd Kammer et al. 2020 Table C-2. VOC Emissions Factors from literature Farm Type Structure Type VOC Emission Factor Unit of Emission Factor Reference Da ry Freestall Barns (cows and feed) Methanol 1.780 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Ethanol 2.010 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Propionic Acid 0.080 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Isobutyric Acid 0.080 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Butyric Acid 0.010 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Isovaleric acid 0.010 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Valeric Acid 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Hexanoic Acid 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Phenol 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) P-Cresol 0.020 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) 4-Ethylphenol 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) 2-Amino-actophenone 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Undole 0.000 Ib/TAU/yr Parker, 2008 Da ry Freestall Barns (cows and feed) Skatole 0.000 Ib/TAU/yr Parker, 2008 D-2 ------- Deliberative, draft document - Do not cite, quote, or distribute Farm Emission Unit of Type Structure Type voc Factor Emission Factor Reference Da ry Openlot (manure and feed) Methanol 4.900 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Ethanol 11.650 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Propionic Acid 3.630 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Isobutyric Acid 0.750 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Butyric Acid 0.090 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Isovaleric acid 0.090 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Valeric Acid 0.110 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Hexanoic Acid 0.340 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Phenol 0.010 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) P-Cresol 0.020 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) 4-Ethylphenol 0.000 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) 2-Amino-actophenone 0.000 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Undole 0.000 Ib/TAU/yr Parker, 2008 Da ry Openlot (manure and feed) Skatole 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Methanol 0.010 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Ethanol 0.040 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Propionic Acid 0.140 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Isobutyric Acid 0.020 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Butyric Acid 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Isovaleric acid 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Valeric Acid 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Hexanoic Acid 0.000 Ib/TAU/yr Parker, 2008 D-3 ------- Deliberative, draft document - Do not cite, quote, or distribute Farm Emission Unit of Type Structure Type voc Factor Emission Factor Reference Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Phenol 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) P-Cresol 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) 4-Ethylphenol 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) 2-Amino-actophenone 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Dairy (lagoons, storage ponds, basins) Undole 0.000 Ib/TAU/yr Parker, 2008 Liquid Manure Handling Da ry (lagoons, storage ponds, basins) Skatole 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Methanol 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Ethanol 0.070 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Propionic Acid 0.090 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Isobutyric Acid 0.070 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Butyric Acid 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Isovaleric acid 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Valeric Acid 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Hexanoic Acid 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Phenol 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng P-Cresol 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng 4-Ethylphenol 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng 2-Amino-actophenone 0.000 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Undole 0.010 Ib/TAU/yr Parker, 2008 Da ry solid manure handl ng Skatole 0.000 Ib/TAU/yr Parker, 2008 Sw ne Lagoon Acetaldehyde 0.660 Hg m"2 min 1 Rumsey et al 2012 Sw ne Lagoon Acetone 2.110 ng m"2 min 1 Rumsey et al 2012 Sw ne Lagoon Ethanol 0.590 ng m"2 min 1 Rumsey et al 2012 D-4 ------- Deliberative, draft document - Do not cite, quote, or distribute Farm Type Structure Type voc Emission Factor Unit of Emission Factor Reference Swine Lagoon 2-ethyl-l-hexanol 0.180 Hg m"2 min 1 Rumsey et al 2012 Swine Lagoon Methanol 1.190 Hg m"2 min 1 Rumsey et al 2012 Swine Lagoon MEK 0.560 Hg m"2 min 1 Rumsey et al 2012 Swine Shallow pit Barn Acetaldehyde 0.100 g/d Rumsey et al 2012 Swine Shallow pit Barn Acetone 0.240 g/d Rumsey et al 2012 Swine Shallow pit Barn 2,3-butanedione 0.190 g/d Rumsey et al 2012 Swine Shallow pit Barn Ethanol 0.450 g/d Rumsey et al 2012 Swine Shallow pit Barn Methanol 0.270 g/d Rumsey et al 2012 Swine Shallow pit Barn 4-methylphenol 0.160 g/d Rumsey et al 2012 D-5 ------- Deliberative, draft document - Do not cite, quote, or distribute D.1 References EPA (U.S. Environmental Protection Agency). 2001a. Emissions from Animal Feeding Operations (Draft). EPA Contract No. 68-D6-0011. Washington, D.C. Available on-line at https://www.epa.gov/sites/default/files/2020-10/documents/draftanimalfeed.pdf Feilberg A., D.Z. Lu, A.P.S. Adamsen, M.J. Hansen, K.E.N. Jonassen Odorant emissions from intensive pig production measured by online Proton-Transfer-Reaction Mass Spectrometry Environ. Sci. Technol., 44 (2010), pp. 5894-5900 Heber, A. J., Ni, J.-Q., Lim, T.T., Tao, P.-C., Schmidt, A.M., 2004. Air Emissions from Swine Production Buildings at Barns 7 and 8 - Final Report. Purdue University, West Lafayette, Indiana, 65p (August 9). Kammer, J., C. Decuq, D. Baisnee, R. Ciuraru, F. Lafouge, P. Buysse, S. Bsaibes, B. Henderson, S. M. Cristescu, R. Benabdallah, V. Chandra, B. Durand, O. Fanucci, J. E. Petit, F. Truong, N. Bonnaire, R. Sarda-Esteve, V. Gros, and B. Loubet. "Characterization of Particulate and Gaseous Pollutants from a French Dairy and Sheep Farm." Science of the Total Environment 712 (Apr 10 2020): 135598. https://dx.doi.Org/10.1016/j.scitotenv.2019.135598. Parker, David. 2008. South Lakes Dairy VOC Emission Characterization Report. Available at https ://www.regulations. gov/comment/EP A-HO-QAR-2010-0960-0041 Rumsey, Ian C., Viney P. Aneja, and William A. Lonneman. "Characterizing Non-Methane Volatile Organic Compounds Emissions from a Swine Concentrated Animal Feeding Operation." Atmospheric Environment 47 (2012): 348-57. https://dx.doi.Org/10.1016/j.atmosenv.2011.10.055. Sheraz Gill, Ramon Norman. 2012. Air Pollution Control Officer's Revision of the Dairy VOC Emission Factors. Available online at https://www.vallevair.org/busind/pto/emission factors/2012-Final-Dairy-EE- Report/FinalDairvEFReport(2-23-12).pdf South Coast Air Quailty Management District (SCAQMD).2016. Guidelines for Calculating Emissions from Dairy and Poultry Operations. Available online at http://www.aqmd.gov/docs/default-source/planning/annual-emission- reporting/guidecal cemisdairypoultryoperdecl3.pdf D-l ------- |