Progress 04/01/10 to 03/31/15

Outputs
Target Audience:?Education. High School Visits. Project personnel visited several local high schools (McLane High School, Youthbuild Charter School and Sunnyside High School) to promote student fellowship opportunities, degree programs and research in environmental research. The schools were selected because they serve large number of socioeconomically disadvantaged and minority students. The visits featured presentations by students, who talked about their experiences working on the project. Project personnel also organized and participated in week long summer camps for high school students and a six day summer workshop for middle/high school teachers in Years 2-4. For both events, the goal was to promote interest in and understanding of science. The project also supported two Circuit Science events held on the Fresno State campus during Spring semesters (Years 2-4). These events featured hands on interactive demonstrations to promote science to elementary and middle school students. Collectively these outreach efforts impacted in excess of 1,600 K-12 students and teachers. Summer Air Quality Internship. In Year 1, three high school students participated in a paid eight-week summer internship program through a leveraged grant from the Fresno Regional Foundation. Selected students spent four weeks working on the project (including one of the field campaigns conducted in August 2010), and then spent four weeks at a regional non-profit organization learning about the environmental legislative process in California. The students had the opportunity to meet state legislators in Sacramento as part of the internship. Each intern also prepared a presentation to be given to classmates on returning to their high schools in the Fall. The fellowships were widely advertised in the local school system, concentrating on schools serving the target demographic, and received over 35 applications for the three available positions. Student Councilor Meeting. The project PI and co-PI helped organize and participated in a half-day informational meeting for high school and community college councilors held at Fresno State during Fall 2010. The goal of the meeting was to raise awareness of STEM scholarships, programs and career opportunities among councilors to promote better advising to students. Councilors were provided with information on Fresno State programs, and the participants toured several of the research laboratories on campus. Fourteen councilors participated in the event. Community College Presentations. Project personnel gave presentations to the student science clubs at two local community colleges (Fresno City College and Reedley College) during Fall 2010. The presentations discussed scholarship and fellowship opportunities in STEM fields, and presented preliminary results from the project. Approximately 100 community college students attended the presentations. Formal Classroom Instruction. Data collected in the project were incorporated into several courses (CHEM 240T - Atmospheric Chemistry; CHEM 110B - Thermodynamics; CHEM 1A - General Chemistry) at Fresno State to raise awareness of the science of agricultural air quality. These courses were taken by almost 500 undergraduate and graduate students over the lifetime of the project. Industry/Regulators. Project personnel met with members of the Agricultural Technology Committee of the San Joaquin Air Pollution Control District to discuss the project prior to the first field measurements and disseminate results.? Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?In addition to the research training provided to students directly through the project's research activities, 16 students spent 1-3 months during the summer of Years 1-3 at the National Laboratory for Agriculture and the Environment (NLAE) in Ames, IA. Students received training in agricultural air quality and micrometeorological research, working with several scientists at this USDA-ARS facility. Students also had the opportunity to present their work at a number of local, regional and national meetings.? How have the results been disseminated to communities of interest?This work has been disseminated in the usual way in journal articles and at scientific meetings. Some results have been presented to representatives at the local air district. Results from this project were also presented to the campus and local community at open house events for undergraduate student research. Project personnel participated in summer workshops for middle and high school teachers and students. They also participated in several on-campus events for elementary and middle school students to promote math and science. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? 1. Evaluate the impact of typical dairy operations on regional air quality We have conducted about 10 field campaigns covering different seasons at two different dairy facilities in the San Joaquin Valley using a range of instrumentation (GC-MS, PTR-MS, SIFT-MS, GC-FID, IR-PAD, diode laser spectroscopy, PILS-IC) and multiple platforms (flux chamber, flow tube, 10-m tower and airborne). We have identified over 100 compounds emitted from dairy sources and have quantified emissions for many of these using different approaches (see below). Alcohols, carbonyls, carboxylic acids and terpenes are the classes of VOC emitted in greatest quantities. Alcohols and terpenes (when present) have the greatest impact on ozone formation. In addition we have quantified NOx emissions from dairy feed sources and identified ensiling as an important source of NOx and VOCs during the brief period that it occurs. 2. Compare three common methods for emissions measurements. We have calculated VOC emissions using a flux chamber, a flow tube, and from upwind/downwind ambient concentrations using both AERMOD (a Gaussian plume model) and WindTrax (a backward stochastic Lagrangian model). Emissions calculated using the isolation methods (flux chamber and flow tube) are systematically lower than those calculated using the models. However, when emissions calculated from isolation method data are adjusted to account for wind speed during the sampling period, the methods agree to within 50%. 3. Compare methods for the analysis of VOCs VOCs were measured using several different sampling (canister, sorbent tube, SPME fiber, tedlar bag) and analysis (GC-MS, GC-FID, PTR-MS, SIFT-MS, IR-PAD and diode laser absorption spectroscopy). With the exception of IR-PAD, these techniques were in good agreement with each other for commonly-measured VOCs. Interferences from water vapor and other chemical species made IR-PAD data consistently unreliable for most VOCs. 4. Prepare a larger and more diverse workforce for scientific careers in agriculture This project has raised awareness of scientific research in agricultural fields for over 1,600 middle and high school students. It has developed course materials taught to over 500 college students, and provided research experiences to dozens of K-12, undergraduate and graduate students. The overwhelming majority of these participants are from groups under-represented in STEM.?

Publications

Progress 04/01/13 to 03/31/14

Outputs
Target Audience: 1. K-12 students educated through outreach events. 2. Undergraduate and graduate research students (both at Fresno State and other local institutions) trained through the research project. 3. Undergraduate students educated through incorporation of project data/methods into course materials. 4. The research community through dissemination of project results. Changes/Problems: Several unforeseeable factors have delayed various aspects of the project, which have resulted in delays: 1. Turnover and loss of staff at the subcontractor site have impacted our capacity to analyze the large number of samples collected during these measurements. The analysis backlog has been exacerbated by instrument failures described in previous reports and issues related to the ‘government shutdown’. 2. Data gathering has been completed, but the model needed for calculating the flux of volatile organic compounds (VOC) from dairy operations are still being developed internally at NLAE. The model is expected to be completed early in the second quarter of 2014 and adatabase is being developed for use with the flux model.These data are also needed as inputs for the regional air quality model. What opportunities for training and professional development has the project provided? Six graduate students and four undergraduate students were trained on the project during this period. Both community college and Fresno State students from three departments (Chemistry, Geography, and Engineering) participated in the collection and analysis of the data. How have the results been disseminated to communities of interest? K-12 Education/Outreach. In Year 4, project personnel visited area high schools to promote student fellowship opportunities, degree programs and research in environmental research. Project personnel also organized and participated in a week long summer camp for high school students and a six day summer workshop for middle/high school teachers. For both events, the goal was to promote interest in and understanding of science. The project also supported several Circuit Science and Stellar Science events held on the Fresno State campus during the academic. These events featured hands on interactive demonstrations to promote science to elementary and middle school students. Collectively these outreach efforts impacted in excess of 1,000 K-12 students and teachers. Formal Classroom Instruction. Data collected in the project were incorporated into several courses (CHEM 110B – Thermodynamics and CHEM 1A – General Chemistry) at Fresno State to raise awareness of the science of agricultural air quality. These courses were taken by over 100 undergraduate students over the course of the project. What do you plan to do during the next reporting period to accomplish the goals? The specific remaining tasks are: 1) Collate VOC and meteorological for eddy covariance calculations. 2) Calculate flux measurements with data available for release. 3) Incorporate flux measurements into WRF Chem to determine regional impacts.

Impacts
What was accomplished under these goals? Method development and implementation. As part of this project, the use of a tethered helium balloon was developed as a platform for collecting atmospheric samples. Samples were collected and analyzed at heights up to 100 m above ground level by attaching sampling media (canisters and sorbent tubes) and sampling lines to the balloon. Our data indicate that this approach can successfully be used to measure profiles of pollutants including VOCs, semi-volatile organics, greenhouse gases and ozone. Flux Method Comparison. Concentrations of selected organics were measured upwind and downwind of the test facility. Emissions were then calculated using back-trajectory calculations, and were compared to flux chamber and wind tunnel measurements. Our data are being used for an intercomparison of these three approaches for calculating fluxes. We have also tested two fundamentally different dispersion models in the backtrajectory calculations. Our data indicate that these methods give equivalent results for flux measurements when used appropriately. Emissions Measurements. The diversity of VOCs emitted from dairy as determined by canister and sorbent tubes increased with temperature. Compounds tended to be polar and multi-functional and concentration/diversity of compounds increased almost two fold comparing January to August. Key chemical classes included alcohols, volatile fatty acids (VFAs), aldehydes, ketones, esters, terpene . Key compounds included ethanol, methanol, propanol, acetic acid, acetone, and acetylaldehyde. There was also evidence of methyl, ethyl, propyl ester formation in silage and TMR. Aromatic compounds such as toluene importance as of percentage total of mass diminished as temperatures increased. A thermal extraction technique was used to characterize both PM10 and PM2.5 material from feedlot and surrounding areas. Odorants such as 4-methylphenol and 3-methyl indole were enriched on the PM compared to gas phase samples and several long chain amide compounds analogous to long chain fatty acids were identified as potential marker compounds from animal production facilities. Levels of greenhouse gases (nitrous oxide, carbon dioxide and methane) have also been measured. Our data are consistent with substantial fluxes of carbon dioxide and methane. Methane emissions are primarily from both dairy cows and waste, while carbon dioxide fluxes are primarily from the animal waste. Methane emissions show little seasonal variation, but carbon dioxide fluxes appear to be highest during the summer months. Nitrous oxide emissions were low throughout the measurement period.

Publications

• Type: Journal Articles Status: Published Year Published: 2013 Citation: " Steven Trabue, Kenwood Scoggin, Hong Li, Robert Burns, Hongwei Xin, Laura McConnell, Richard Gates, Alam Hasson, Segun Ogunjemiyo and Jerry Hatfield, Bias of Non-Methane Hydrocarbon Analyzers in VOC Monitoring for Polar Oxygenated Compounds, Journal of the Air and Waste Management Association 63, 1163-1172 (2013)

Progress 04/01/12 to 03/31/13

Outputs
Target Audience: K-12 Education/Outreach. Approximately 500 K-12 students and teachers Formal Classroom Instruction. Approximately 100 undergraduate students.. Researchers. Members of the research community through conference presentations and journal publications. . Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Training. Six graduate students and twenty one undergraduate students were trained on the project during this period. Both community college and Fresno State students from six departments (Chemistry, Geography, Biology, Physics, Earth and Environmental Science, and Engineering) participated in the collection and analysis of the data. Five Fresno State students spent one month at the National Laboratory for Agriculture and the Environment (NLAE) during summer 2012, where they received additional training in agricultural air quality research. A sixth student spent three months at NLAE as an intern. How have the results been disseminated to communities of interest? K-12 Education/Outreach. In Year 3, project personnel visited a high school (Sunnyside High School) to promote student fellowship opportunities, degree programs and research in environmental research. The school was selected because it serves a large number of socioeconomically disadvantaged and minority students. Project personnel also organized and participated in a week long summer camp for high school students and a six day summer workshop for middle/high school teachers. For both events, the goal was to promote interest in and understanding of science. The project also supported two Circuit Science events held on the Fresno State campus during Spring 2012. These events featured hands on interactive demonstrations to promote science to elementary and middle school students. Collectively these outreach efforts impacted in excess of 500 K-12 students and teachers. Formal Classroom Instruction. Data collected in the project were incorporated into several courses (CHEM 110B – Thermodynamics and CHEM 1A – General Chemistry) at Fresno State to raise awareness of the science of agricultural air quality. These courses were taken by over 100 undergraduate students over the course of the project. What do you plan to do during the next reporting period to accomplish the goals? The specific tasks to be accomplished during the next reporting period are: 1) Collect limited number of additional samples for analysis by PTRMS at Fresno State dairy. 2) Complete processing and analysis of measured concentrations of ozone, particulate matter, ammonia, methane, nitrous oxide, and volatile organic compounds (VOCs). a) Measurements from balloon sampling for ozone, greenhouse gases, and VOCs b) Measurements from environmental flux chambers for animal feed c) Canister and sorbent tube data for over 50 VOCs d) Measurements with low-volume samplers for PM10 and PM2.5 and speciation of sorbed VOC. 3) Complete calculation of emission fluxes for VOCs using the flux-gradient technique and inverse modeling. 4) Complete regional modeling of air quality impacts with WRF Chem.

Impacts
What was accomplished under these goals? Field measurements. Five sets of field measurements were carried out during Year 3 of the project at a commercial dairy in Kings County, CA. In each set of measurements, samples were collected using evacuated canisters and sorbent tubes, and were analyzed using gas chromatography-mass spectrometry. Samples were also analyzed in-situ with infra-red photoaccoustic detectors, an ozonesonde, a NOx chemiluminescence analyzer, a UV absorption ozone analyzer, IR lasers, methane analyzers (gas chromatography with flame ionization detection), a selective ion flow tube mass spectrometer (SIFT-MS) and a proton transfer reaction mass spectrometer (PTR-MS). A range of meteorological data were also collected. Three platforms were used to obtain samples: flux chambers, a 10 m tower located at the downwind edge of the facility, and a tethersonde (which collected samples up to 200 m) located adjacent to the tower. Additional longer term (4 months) measurements using an array of sampling lines at different locations were used to measure emissions during the construction of a silage pile and the subsequent storage of the silage. Modeling. AERMOD and Wind Trax were used to model VOC emissions during the first sets of field measurements. The data were compared to flux chamber measurements to evaluate the predicted fluxes using these methods. Preliminary work was also carried out to install WRF Chem on a local computational cluster at Fresno State. This will be used to carry out regional air quality modeling. Student Training. Approximately thirty students (including high school, undergraduate and graduate level students) received training in the field of agricultural air quality measurements and techniques. Method development and implementation. As part of this project, the use of a tethered helium balloon was developed as a platform for collecting atmospheric samples. Samples were collected and analyzed at heights up to 100 m above ground level by attaching sampling media (canisters and sorbent tubes) and sampling lines to the balloon. Our data indicate that this approach can successfully be used to measure profiles of pollutants including VOCs, semi-volatile organics, greenhouse gases and ozone. Flux Method Comparison. Concentrations of selected organics were measured upwind and downwind of the test facility. Emissions were then calculated using back-trajectory calculations, and were compared to flux chamber and wind tunnel measurements. Our data are being used for an intercomparison of these three approaches for calculating fluxes. We have also tested two fundamentally different dispersion models in the backtrajectory calculations. Our data indicate that these methods give equivalent results for flux measurements when used appropriately. Emissions Measurements. The diversity of VOCs emitted from dairy as determined by canister and sorbent tubes increased with temperature. Compounds tended to be polar and multi-functional and concentration/diversity of compounds increased almost two fold comparing January to August. Key chemical classes included alcohols, volatile fatty acids (VFAs), aldehydes, ketones, esters, terpene . Key compounds included ethanol, methanol, propanol, acetic acid, acetone, and acetylaldehyde. There was also evidence of methyl, ethyl, propyl ester formation in silage and TMR. Aromatic compounds such as toluene importance as of percentage total of mass diminished as temperatures increased. Thermal extraction technique was used to characterize both PM10 and PM2.5 material from feedlot and surrounding areas. Odorants such as 4-methylphenol and 3-methyl indole were enriched on the PM compared to gas phase samples and several long chain amide compounds analogous to long chain fatty acids were identified as potential marker compounds from animal production facilities. Levels of greenhouse gases (nitrous oxide, carbon dioxide and methane) have also been measured. Our data are consistent with substantial fluxes of carbon dioxide and methane. Methane emissions are primarily from the dairy cows, while carbon dioxide fluxes are primarily from the animal waste. Methane emissions show little seasonal variation, but carbon dioxide fluxes appear to be highest during the summer months. Nitrous oxide emissions were low throughout the measurement period. Concentrations of ozone, NO and NO2 were also measured during this reporting period. Levels of NO were found to be unexpectedly high during the summer, and our subsequent analysis has shown that farm machinery rather than silage is the likely source of this NO. However, recent measurements made during the construction of a silage pile suggest that silage may be a large source of NOx for several days during this process.

Publications

• Type: Journal Articles Status: Published Year Published: 2013 Citation: Alam S. Hasson*, Segun O. Ogunjemiyo, Steven Trabue, Shawn Ashkan, Kenwood Scoggin, Julie Steele, Catalina Olea, Srikar Middala, Kennedy Vu, Austen Scruggs, Laxmi R. Addala, Lucien Nana, NOx emissions from a Central California Dairy, Atmos. Environ., 70, 328-336 (2013).
• Type: Journal Articles Status: Accepted Year Published: 2013 Citation: Steven Trabue, Kenwood Scoggin, Hong Li, Robert Burns, Hongwei Xin, Laura McConnell, Richard Gates, Alam Hasson, Segun Ogunjemiyo and Jerry Hatfield, Bias of Non-Methane Hydrocarbon Analyzers in VOC Monitoring for Polar Oxygenated Compounds, Journal of the Air and Waste Management Association
• Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Alam S. Hasson, Segun O. Ogunjemiyo, Steven Trabue, Shawn Ashkan, Catalina Olea, Srikar Middala, Kennedy Vu, Austen Scruggs, Laxmi R Addala, Lucien Nana, Julie Steele and Thomas Shelton, Emissions of ozone precursors from a central California dairy facility, American Chemical Society National Fall Meeting, Philadelphia PA, August 19-23, 2012.
• Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Steven Trabue, Kenwood Scoggin, Laura McConnell, Ronaldo Maghirang, Alam Hasson, Segun Ogunjemiyo, Characterizing Carbonaceous Materials Emitted from Animal Feeding Operations, American Association of Aerosol Research, Minneapolis MN, October 8-12, 2012.
• Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Alam Hasson, Segun Ogunjemiyo and Steven Trabue, Greenhouse Gas Measurements at a Central California Dairy, 2013 California Plant and Soil Conference, Visalia CA, February 7-8, 2013.

Progress 04/01/11 to 03/31/12

Outputs
OUTPUTS: Field measurements. Three sets of field measurements were carried out in the second year of the project at a commercial dairy in Kings County, CA. In each set of measurements, samples were collected using evacuated canisters and sorbent tubes, and were analyzed using gas chromatography-mass spectrometry. Samples were also analyzed in-situ with infra-red photoaccoustic detectors, an ozonesonde, a NOx chemiluminescence analyzer, a UV absorption ozone analyzer, IR lasers and a range of meteorological data were also collected. Three platforms were used to obtain samples: flux chambers, a 10 m tower located at the downwind edge of the facility, and a tethersonde (which collected samples up to 200 m) located adjacent to the tower. Modeling. AERMOD was used to model VOC emissions during the first set of field measurements. The data were compared to flux chamber measurements to evaluate the predicted fluxes using these methods. Preliminary work was also carried out to install WRF Chem on a local computational cluster at Fresno State. This will be used to carry out regional air quality modeling in Year 3 of the project. Student Training. Approximately twenty students (including high school, undergraduate and graduate level students) received training in the field of agricultural air quality measurements and techniques. Dissemination. Data from the field campaigns were presented at several professional meetings: 29th Informal Symposium on Kinetics and Photochemical Processes in the Atmosphere, CSU Fullerton, February 24th, 2012. American Association of Geographers Annual Meeting, New York City, NY, February 24-8, 2012. American Chemical Society National Spring Meeting, San Diego CA, March 25-9, 2012. Results from this project were also presented to the campus and local community at an open house for undergraduate student research. Project personnel participated in summer workshops for middle and high school teachers and students. They also participated in several on-campus events for elementary and middle school students to promote math and science. PARTICIPANTS: Individuals Dr. Alam Hasson (PI). Dr. Hasson oversaw all aspects of the project including planning and implementation of the project components, recruitment and training of students, coordination of the participating investigators, data analysis and synthesis, and dissemination of project outcomes. Dr. Segun Ogunjemiyo (co-PI). Dr. Ogunjemiyo oversaw the operation of the helium balloon to collect field samples, and the collection and analysis of ozone concentrations and meteorological data. He also trained several students in micrometeorological methods and data analysis. Dr. Steven Trabue (co-PI). Dr. Trabue directed the project activities conducted at the National Laboratory for Agriculture and the Environment. He collected and analyzed canister and sorbent tube samples during the field measurement campaign. He also supervised the training of the six Fresno State students that visited his laboratory during summer 2011. Mr. Shawn Ashkan. Mr. Ashkan coordinated the field campaigns conducted at two dairies. He was responsible for equipment and site preparation. He was also the project liaison with the local dairy industry, and he participated in several air district meetings on behalf of the project. Students. Nine students received significant support from the project. The students assisted Mr. Ashkan in preparing the sampling sites, and were responsible for the collection and analysis of samples under the supervision of the PI and co-PIs. Collaborators and Contacts Dr. Philip Silva (USDA-ARS) and Dr. Kathleen Purvis-Roberts (Claremont Colleges). Drs. Silva and Purvis-Roberts are conducting research to investigate the chemistry of amines and its role in the formation of particulate matter. Dr. Purvis-Roberts participated in our May 2011 field campaign, training two undergraduate students, and will participate in additional campaigns. Dr. Silva participated in our January 2012 measurements. Dr. John Prueger (National Laboratory for Agriculture and the Environment). Dr. Prueger, a respected authority on micrometeorology, participated in the January 2012 measurements and has deployed several instruments that will be used during the project. His expertise will assist us in further constraining the emissions calculated from the data collected. Dr. Gabrielle Pfister (National Center for Atmospheric Research) and Dr. Marcelo Mena (Universidad Andres Bello, Chile). Dr. Pfister is an internationally-renowned atmospheric chemistry modeling expert who has worked on Central California air quality issues. Dr. Mena is an air quality modeling expert who has worked extensively with the WRF Chem model. He spent the 2010-11 academic year at Fresno State on a Fulbright scholarship. Both are expected to work with project personnel on the regional modeling component of the project. Professional Development. Four of the students supported by this project also received training at the National Laboratory for Agriculture and the Environment during summer 2011, providing them with work experience in a USDA-ARS lab. These students participated in additional measurements at a cattle feedlot in Kansas during this period. TARGET AUDIENCES: Education. K-12 Education/Outreach. Project personnel visited a high school (Youthbuild Charter School) to promote student fellowship opportunities, degree programs and research in environmental research. The school was selected because it serves a large number of socioeconomically disadvantaged and minority students. Project personnel also organized and participated in a week long summer camp for high school students and a six day summer workshop for middle/high school teachers. For both events, the goal was to promote interest in and understanding of science. The project also supported two `circuit science' events held on the Fresno State campus during Spring 2012. These events featured hands on interactive demonstrations to promote science to elementary and middle school students. Collectively these outreach efforts impacted in excess of 500 K-12 students and teachers. Formal Classroom Instruction. Data collected in the project were incorporated into several courses (CHEM 110B - Thermodynamics and CHEM 1A - General Chemistry) at Fresno State to raise awareness of the science of agricultural air quality. These courses were taken by over 140 undergraduate students. Industry/Regulators. Project personnel participated in the Agricultural Technology Committee meetings of the San Joaquin Air Pollution Control District. Results from the project will be disseminated to both regulators and the dairy industry through this committee as these outputs become available. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Method development and implementation. As part of this project, the use of a tethered helium balloon was developed as a platform for collecting atmospheric samples. Samples were collected and analyzed at heights up to 100 m above ground level by attaching sampling media (canisters and sorbent tubes) and sampling lines to the balloon. Our data indicate that this approach can successfully be used to measure profiles of pollutants including VOCs, semi-volatile organics, greenhouse gases and ozone. Method Comparison. Concentrations of selected organics were measured upwind and downwind of the test facility. Emissions were then calculated using back-trajectory calculations, and were compared to flux chamber and wind tunnel measurements. Additional work is in progress to evaluate differences in flux chamber, upwind/downwind, and gradient flux measurements. Emissions Measurements. Over 100 organics have been identified and quantified in the samples collected. The dominant organics emitted are alcohols and short-chain carboxylic acids, with significant quantities of aldehydes, ketones, esters and some aromatics also present. Previous measurements have identified ethanol and acetic acid as the major organics present. Our work shows that larger alcohols and carboxylic acids may also be present at significant levels. Our observations of significant fluxes of esters also add to the existing literature. Levels of greenhouse gases (nitrous oxide, carbon dioxide and methane) have also been measured. Our data are consistent with large fluxes of carbon dioxide and methane, although these data are still being analyzed. Concentrations of ozone, NO and NO2 were also measured during this reporting period. Levels of NO were found to be unexpectedly high during the summer, and our subsequent analysis has shown that silage is emitting significant quantities of NO. While this has been observed in one European study, we are unaware of any measurements of this kind in the US. Since ozone formation is NOx limited in much of Central California, this is a potentially important finding that will be further explored during the project period. Training. Four graduate students and sixteen undergraduate students were trained on the project during this period. Both community college and Fresno State students from six departments (Chemistry, Geography, Biology, Physics, Earth and Environmental Science, and Engineering) participated in the collection and analysis of the data. Four Fresno State students spent one month at the National Laboratory for Agriculture and the Environment during summer 2011, where they received additional training in agricultural air quality research.

Publications

• Vertical Ozone and Boundary Layer Profiles at a Dairy Facility in Central California, Segun Ogunjemiyo, Julie Steele, Thomas Shelton, Ryan Mchenry, Brenda Osborne, Alam Hasson and Shawn Ashkan, American Association of Geographers Annual Meeting, New York, NY, February 24-28 2012.
• Emissions of volatile organics, greenhouse gases and particulate matter precursors from dairy facilities in Central California, Alam S Hasson, Segun O Ogunjemiyo, Steven Trabue, Catalina Olea, Shawn Ashkan, Kenwood Scoggin, Srikar Middala, Kennedy Vu, Laxmi R Addala, Lucien Nana, Julie Steele and Thomas Shelton, American Chemical Society National Meeting, San Diego, CA, March 25-29 2012.

Progress 04/01/10 to 03/31/11

Outputs
OUTPUTS: Field measurements. Two sets of field measurements were carried out during the first year of the project. The first set of measurements was carried out at the University dairy on the California State University, Fresno campus during August 2010. A second field campaign took place at a commercial dairy during April 2010. In each set of measurements, samples were collected using evacuated canisters and sorbent tubes, and were analyzed using gas chromatography-mass spectrometry. Samples were also analyzed in-situ with infra-red photoaccoustic detectors and an ozonesonde, and a range of meteorological data were also collected. Three platforms were used to obtain samples: flux chambers, a 10 m tower located at the downwind edge of the facility, and a tethersonde (which collected samples up to 200 m) located adjacent to the tower. Lab Measurements. The atmospheric chemistry of several esters (which were observed in dairy emissions at relatively high levels) was investigated in a reaction chamber. Changes in the concentrations of reactants and products were monitored by long path Fourier Transform Infrared (FTIR) spectroscopy. The data were used to elucidate the reaction mechanism and thus the behavior of the pollutant in the atmosphere. Modeling. AERMOD was used to model VOC emissions during the first set of field measurements in August 2010. The data were compared to flux chamber measurements to evaluate the predicted fluxes using these methods. Student Training. Approximately twenty students (including high school, undergraduate and graduate level students) received training in the field of agricultural air quality measurements and techniques. Dissemination. Preliminary data from the first field campaign were presented at a regional scientific meeting (28th Informal Symposium on Kinetics and Photochemical Processes in the Atmosphere, UC Irvine, March 3rd, 2011). Several students presented work from this study at a regional meeting attended by a large number of community members (32nd Central California Research Symposium, April 6th 2011). Presentations were also given to the science clubs at two local community colleges (Fresno City College and Reedley College) and two high schools (Youthbuild Charter School and McLane High School). Project personnel also met with members of the Agricultural Technology Committee of the San Joaquin Air Pollution Control District to discuss the project. The committee includes regulators, agricultural industry representatives and environmental groups. The project was the subject of a five-minute video produced by Fresno State's Agricultural Research Initiative, which has been posted on Youtube. The video explains the goals of the project and outlines the activities that are ongoing to answer these questions to a general audience. The work was also featured in an article in the Fresno Bee, the local newspaper. The article was picked up and printed by a number of other papers within the region. PARTICIPANTS: Dr. Alam Hasson (PI). Dr. Hasson oversaw all aspects of the project including planning and implementation of the project components, recruitment and training of students, coordination of the participating investigators, data analysis and synthesis, and dissemination of project outcomes. Dr. Segun Ogunjemiyo (co-PI). Dr. Ogunjemiyo oversaw the operation of the helium balloon to collect field samples, and the collection and analysis of ozone concentrations and meteorological data. He also trained several students in micrometeorological methods and data analysis. Dr. Steven Trabue (co-PI). Dr. Trabue directed the project activities conducted at the National Laboratory for Agriculture and the Environment. He collected and analyzed canister and sorbent tube samples during the field measurement campaign. He also supervised the training of the six Fresno State students that visited his laboratory during summer 2010. Mr. Shawn Ashkan. Mr. Ashkan coordinated the field campaigns conducted at two dairies. He was responsible for equipment and site preparation. He was also the project liaison with the local dairy industry, and he participated in several air district meetings on behalf of the project. Students (Catalina Olea, Austen Scruggs, Lucien Nana, Kennedy Vu, Sarah Huber, Julie Steele and Srikar Middala). Seven students received significant support from the project. The students assisted Mr. Ashkan in preparing the sampling sites, and were responsible for the collection and analysis of samples under the supervision of the PI and co-PIs. Partner Organizations Fresno Regional Foundation (FRF). FRF is "a non-profit community foundation that invests in programs to address economic, social, educational, cultural and environmental needs". FRF provided funding during 2009-10 that enabled three high school students to participate in a summer research internship at Fresno State. The students participated in the field campaign at the Fresno State dairy and learned about agricultural air quality research. Agricultural Research Initiative (ARI). ARI is "a comprehensive applied agricultural and environmental research program joining the California State University's four colleges of agriculture and the state's agriculture and natural resources industries and allied business communities". The PI and co-PI received funding from ARI in March 2011 to measure greenhouse gas emissions from dairies, leveraging the USDA award. Collaborators and Contacts Dr. Philip Silva (USDA-ARS) and Dr. Kathleen Purvis-Roberts (Claremont Colleges). Drs. Silva and Purvis-Roberts are conducting research to investigate the chemistry of amines and its role in the formation of particulate matter. The researchers plan to deploy some instrumentation at the project's sampling site during Year 2 of the project. Professional Development. Six of the students supported by this project also received training at the National Laboratory for Agriculture and the Environment during summer 2010, providing them with work experience in a USDA-ARS lab. Four of these students participated in additional measurements at a cattle feedlot in Kansas during this period. TARGET AUDIENCES: Education. High School Visits. Project personnel visited two high schools (McLane High School and Youthbuild Charter School) to promote student fellowship opportunities, degree programs and research in environmental research. The schools were selected because they serve large number of socioeconomically disadvantaged and minority students. The visits featured presentations by students, who talked about their experiences working on the project. A total of 140 high school students were impacted by these activities. Summer Air Quality Internship. Three high school students participated in a paid eight-week summer internship program through a leveraged grant from the Fresno Regional Foundation. Selected students spent four weeks working on the project (including one of the field campaigns conducted in August 2010), and then spent four weeks at a regional non-profit organization learning about the environmental legislative process in California. The students had the opportunity to meet state legislators in Sacramento as part of the internship. Each intern also prepared a presentation to be given to classmates on returning to their high schools in the Fall. The fellowships were widely advertised in the local school system, concentrating on schools serving the target demographic, and received over 35 applications for the three available positions. Student Councilor Meeting. The project PI and co-PI helped organize and participated in a half-day informational meeting for high school and community college councilors held at Fresno State during Fall 2010. The goal of the meeting was to raise awareness of STEM scholarships, programs and career opportunities among councilors to promote better advising to students. Councilors were provided with information on Fresno State programs, and the participants toured several of the research laboratories on campus. Fourteen councilors participated in the event. Community College Presentations. Project personnel gave presentations to the student science clubs at two local community colleges (Fresno City College and Reedley College) during Fall 2010. The presentations discussed scholarship and fellowship opportunities in STEM fields, and presented preliminary results from the project. Approximately 100 community college students attended the presentations. Formal Classroom Instruction. Data collected in the project were incorporated into several courses (CHEM 240T - Atmospheric Chemistry; CHEM 110B - Thermodynamics; CHEM 1A - General Chemistry) at Fresno State to raise awareness of the science of agricultural air quality. These courses were taken by over 130 undergraduate and graduate students. Industry/Regulators. Project personnel met with members of the Agricultural Technology Committee of the San Joaquin Air Pollution Control District to discuss the project prior to the first field measurements. Results from the project will be disseminated to both regulators and the dairy industry through this committee as these outputs become available. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Method development. As part of this project, the use of a tethered helium balloon was developed as a platform for collecting atmospheric samples. Samples were collected and analyzed at heights up to 100 m above ground level by attaching sampling media (canisters and sorbent tubes) and sampling lines to the balloon. The preliminary data indicate that this approach can successfully be used to measure profiles of pollutants including VOCs, semi-volatile organics, greenhouse gases and ozone. Method Comparison. Concentrations of selected organics were measured upwind and downwind of the test facility. Emissions were then calculated using back-trajectory calculations, and were compared to flux chamber measurements. Preliminary analysis indicates that the agreement between the two flux measurements is generally good, implying that the emissions reported in other studies using flux chamber measurements are likely reliable. Additional work is in progress to evaluate differences in flux chamber, upwind/downwind, and gradient flux measurements. Emissions Measurements. Over 100 organics have been identified and quantified in the samples collected. The dominant organics emitted are alcohols and short-chain carboxylic acids, with significant quantities of aldehydes, ketones, esters and some aromatics also present. Emissions are higher from feed than waste sources, consistent with previous work. At the first test site, ambient concentrations are highest in the early evening (4-8 pm). Preliminary modeling indicates that this can be explained by meteorology, and that changes in emissions due to animal activity or specific facility operations are not needed to account for this temporal behavior. Training. Four graduate students, sixteen undergraduate students and three high school students were trained on the project. Both community college and Fresno State students from six departments (Chemistry, Geography, Biology, Physics, Earth and Environmental Science, and Engineering) participated in the collection and analysis of the data. Six Fresno State students spent one month at the National Laboratory for Agriculture and the Environment during summer 2010, where they received additional training in agricultural air quality research.

Publications

• No publications reported this period