## Dairy Operations: An Evaluation and Comparison of Baseline and Potential Mitigation Practices for Emissions Reductions In the San Joaquin Valley

FINAL REPORT

Principal Investigator:

Dr. Charles Krauter California State University - Fresno

Co-Principal Investigator: Dr. Donald Blake University of Ca lifornia - Irvine

California Air Resources Board Contract No. 04-343 Project administered as CSU Fr esno Foundation Project #37411

Submitted May 1, 2009 Prepared for the California Air Resources Board and the California Environmental Protection AgencyDisclaimer

The statements and conclusions in this r eport are those of the Contractor and not necessarily those of the Calif ornia Air Resources Board. The mention of commercial products, their source, or their use in c onnection with material herein is not to be construed as actual or implied endorsement of such products.

NOTE: This project was proposed in respon se to a request by the California Air Resources Board for a monitoring study to determine the sources and species of ROG emissions from dairy operations. A data se t was to be collected that would serve to validate processes that might reduce emissi ons and provide a broader base of data for facility and regional modeling. After the study was approved and began the initial stages of selecting sites and sampling met hods; there were requests from other agencies and researchers to cooperate and add s upport to make the project larger in scope and extend the time to increase the am ount and value of the data collected. One of the secondary objectives of the CARB proposal was to solicit just such augmentation to the original work. The net result of t hese additions to the project was positive in all respects but one. The additional, related projects are not scheduled to be completed until 2009 or 2010. The terms of the CARB resear ch contract require a draft final report for review by January, 2009 and a final vers ion of the report by May, 2009. A considerable amount of field work remain s to be completed and much more data has yet to be analyzed from these related proj ects. Consequently, only data and results from the original CARB cont ract work will be r eported here. That data comes from the analysis done by Dr. Blake at UC Irvine. Th e related projects have added air samples analyzed at CSU Fresno, analysis of alc ohols, N compounds and greenhouse gasses, sampling and analysis of feed, silage, manure, soils and ot her materials to correlate with flux rates monitored at the dairy sites. This additional data is not yet complete and cannot be reported here. In several instances, UC Irvine data cannot be completely evaluated until those related pr ojects are complete. A comprehensive report will be prepared by the end of 2009 to include all the data reported here along with the additional results from t he related projects.

iiAcknowledgements: The field work portion of this project was conducted by students and staff in the Plant Science Department and the Center for Irrigation Technology at CSU Fresno. The following CIT staff supervised the sampling and other data collection activities at the dairy locations: Shawn Ashkan – Research Scientist and Agricultural Engineer Matt Beene – former Research Scientist, now R&D director for Helena Chemical Co. Barry Goodrich – former Research Scientist, now a doctoral student at Texas A&M. Plant Science Department students: Jon Thornton, Martin Brito, Robbie Massera

Analytical work for the project was conducted in the Chemistry Department at UC Irvine under the direction of Dr. Donald Blake. A doctoral student, Melissa Yang, supervised the sample custody, analysis and reporting of data back to CSU Fresno.

The Principle Investigators gratefully acknowledge the unknown member of the CARB RSC who suggested the collaboration with UC Irvine upon review of the original proposal submitted by CSU Fresno.

The Dairy Sub-committee, formed by CARB and CDFA in 2002 and reconstituted by the SJVAPCD in 2005 became the advisory group for this project. The original proposal and all subsequent revisions described below were suggested and approved by this advisory group. The Dairy Sub-committee members directly and actively involved in this project were:
Public Agency members: California Air Resources Board: Patrick Gaffney, Michael FitzGibbon and Dale Shimp California Department of Food and Agriculture: Matt Summers and Rolf Frankenbach San Joaquin Valley Air Pollution Control District: Dave Mitchell, James Sweet and Sheraz Gill USDA-NRCS: John Beyer and Johnnie Siliznoff
Dairy and Agricultural Industry members: Dairy CARES: J. P. Cativiela Western United Dairymen: Paul Martin California Dairy Campaign: Kevin Abernathy Hilmar Cheese Co: Denise Mullinax Nisei Farmers League: Manual Cunha Dairy Operators: George Longfellow and Simon Vander Woude

Research members UC Davis: Dr. Frank Mitloehner and Dr. Deanne Meyer U New Hampshire: Dr. Bill Salas and Dr. Changshen Li Texas A&M: Dr. Calvin Parnel, Dr . Bryan Shaw and Barry Goodrich

The investigators would most like to acknowledge the cooperation of six anonymous dairy operators who allowed us frequent access to their dairies, often with little notice, and never failed to help us when we needed it.

This Report was submitted in fulfillment of California Air Resources Board Contract No. 04-343 for the project titled “Dairy Oper ations: An Evaluation and Comparison of Baseline and Potential Mitigation Practice s for Emissions Reductions In the San Joaquin Valley” administered as CSU Fr esno Foundation Project #37411 under the partial sponsorship of the California Air Res ources Board. Work on the portion of the project reported here was comp leted as of January, 2009

iii

### Table of Contents Page

Disclaimer ................................................................................................. ii Acknowledgem ents ................................................................................... iii
List of T ables .............................................................................................. v
List of Fi gures ............................................................................................. v Glossary of terms, abbreviati ons and symbols and units .......................... vi
Abstract .................................................................................................... viii
Executive Su mmary .................................................................................. ix
Introducti on ................................................................................................ 1
Materials and Methods ............................................................................... 2
Ob jectives ............................................................................................ 2
Field Sa mpling Over view ...................................................................... 5 Quality Assu rance Object ives .............................................................. 5 Sample Coordination and Recording .................................................... 6
Calibrati on Procedur es ......................................................................... 6 Data Reduction, Validation and Reporting ........................................... 6 Samp ling Si tes .................................................................................... 7 Dairy Descripti ons ................................................................................ 8 Regular Samp ling Program, Year-2 ..................................................... 9
Result s ..................................................................................................... 18 Silage Flux Rates ............................................................................... 19
Feed Flux Ra tes ................................................................................. 21
Flush Lane Flux Ra tes ....................................................................... 24 Open Lo t Flux Ra tes .......................................................................... 26
Correlations With Ambient Condi tions ............................................... 27
Discussio n ................................................................................................ 28 Summary and Conc lusions ...................................................................... 33
Recommendat ions ................................................................................... 36
References ............................................................................................... 37
Inventions and Publications ...................................................................... 37 Appendix A. Individual Samples From Dairy Oper ations ......................... 38 Appendix B. Year-1 Progress Re port ....................................................... 45 Appendix C. Organics A nalysis Descrip tion ............................................ 61 Appendix D. Flux Ch amber Methodology and Sample Log Sheets........66

ivList of Figures Page Figure 1. Flux chamber sampling of an open lot area at Dairy B. 13 Figure 2. Flux chambers on a flush l ane at Dairy B. 14 Figure 3. Flux chambers sampling Tota l Mixed Ration at Dairy A. 15 Figure 4. Flux chamber sampling of silage at Dairy D. 16 Figure 5. Flux chamber field blank at Da iry F. 17 Figure 6. Total ROG fluxes relate d to time after feed placement. 23 Figure 7. Total Alcohol fluxes related to time after feed pl acement. 24 Figure 8. ROG fluxes averaged from each dairy and sampling date. 30 Figure 9. Fluxes of 6 prominent ROG components in feed and silage. 31 Figure 10. An example of ROG source magnitudes at a fictit ious dairy. 35

List of Tables Page
Table 1. Modified Year-2 monitori ng program adopted for Fall-07. 11 Table 2. Special Sampling program proposed for Year-2. 12 Table 3. Average flux rates for “d isturbed silage” material. 20 Table 4. Average flux rates for “ undisturbed silage” material. 21 Table 5. Average TMR flux rates for all daires. 22 Table 6. Average TMR flux rates fo r each dairy sampled. 23 Table 7. Average flush lane flux rates. 25 Table 8. Average flush lane flux ra tes with questionable data deleted. 26 Table 9. Open lot, exercise pen and co rral flux averages. 27 Table 10. Average flux rates for all dairies, dat es and operations. 29 Table A1. Silage samples from materi al dislodged from the pile. 39 Table A2. Silage samples from undisturbed material. 40 Table A3. Individual samples of feed (TMR) fluxes. 41
Table A4. Individual flush lane fluxes. 42 Table A5. Open lot, exercise pen and corral fluxes. 43 Table A6. Ambient samples taken prior to July, 2007. 44

v

### Glossary of terms, abbreviations, symbols and units

General terms

CARB – California Air Resources Board CDFA – California Department of Food and Agriculture CSU Fresno – California St ate University at Fresno Dairy sub-committee – A group formed join tly by CARB and CDFA in 2002 that subsequently became the advisory group for this project. DPAG – Dairy Permitting Advisory Group fo rmed by the SJVAPCD in 2004. Members of the Dairy Sub-committee also participated in this activity. SJVAPCD – San Joaquin Valley Air Pollution Control District UC Davis – University of California at Davis UC Irvine – University of California at Irvine UNH – University of New Hampshire

Dairy terms

Commodities - Purchased components of the TMR such as cottonseed meal, rolled corn, almond hulls, distillers grain, citr us pulp and other materials to add energy and nutrition to the feed. Flush lanes – long sloping, hard-surfac ed lanes upon which the cows stand when feeding. The lanes are washed with a larg e volume of water or scraped several times each day to flush manure into various collection and storage areas. Lagoons – Ponds containing the water from t he flush lanes, generally after separation of coarse manure material. Flus h water is recycled from the lagoon. Manure - The combination of urine and feces eliminated by the dairy cows. Open lots – Corrals, exercise pens and other fenced areas available for the cows adjacent to the barns. Most dairies rest rict access to open lots in wet weather. Silage – Chopped and compressed plant materi al harvested and stored for use in making the TMR. Silage is usually the la rgest component of t he TMR. Typically made from field corn, it is also made from alfalfa and various small grains and referred to as “grass” or “winter” silage. TMR - Total mixed ration is t he term for the feed mixture m ade from silage, alfalfa hay and various commodities. TMR is usually mixed at the dairy and delivered from a truck or wagon into a feed bunker. TMR is fed 2-4 times each day. Most dairies employ a nutrition consultant to recommend the specific components of TMR to achieve the desired level of energy and nutriti on for the cows as it relates to their condition, the season and the various commodity prices.

Research terms and units

Alcohols – Ethanol, Methanol and Propanol analyzed by UC Irvine and reported as components of ROG in this report DMS – Di-Methyl Sulfide, a significant co mponent of ROG from some dairy sources. DMDS – Di-Methyl Di-Sulfide, a signific ant component of ROG from some dairy

sources.

viEmissions – In this report, “emissions” is a term used in a general sense to describe the volatile flux of a gas or combination of gasses such as ROG from a surface. The term is not intended to imply an emission rate or emission factor when used in this report. Flux – In this report, “flux” is the term used to describe volatile transfer across the interface between a surface and an atmospher e. This interface can be either surface to ambient atmosphere or su rface to flux chamber atmosphere. Flux rate – In this r eport, “flux rate” refers to the quantitative volume of a flux in units of mass per unit area per unit time. Flux chamber – In this report, “flux cham ber” is the field sampling device described in the US-EPA Isolation Flux Chamber Me thodology (Appendix D). Flux Chambers used in this study covered an area of 0.1924 m 2 and were flushed with zero air at a rate of 10 liters/minute. Flux chambers used in this project were manufactured by Odotech of Toronto, Canada. GC-MS – Gas Chromatography with Mass Spec trometry detection. This is the general term for the method of analysis used by UC Irvine to speciate and quantify the components of the air samples co llected at the dairy sites.
μ g/m 2 /minute – The unit of flux rate used in th is study. Micro-grams per square meter per minute.
μ g/m 3 - The unit of mass per unit volume of air. Micro-grams per cubi c meter. This is the intermediate step in the conversion of proportional volume such as pptV reported in the UC Irvine analysis to mass per unit of air before the calculation of flux rate. ROG – In this report, “Reac tive Organic Gas” is the sum of volatile organic compounds reported from the UC Irvine analysis that are sufficiently reactive to be considered ozone precursors. In this st udy, 60 of the 64 gasses in the UC Irvine analyses were summed and reported as ROG. Methane, CO, CO 2 and acetone were excluded from the R OG total though they were r eported by UC Irvine. The gasses included in the total of ROG are not equally reactive. Some may result in much more ozone than others. No distinction was made in this study with respect to relative reactivity among the ROG ga sses but other contemporary studies are evaluating reactivity with respect to dairy ROG emissions. A complete evaluation of dairy ROG emissions will require the applicat ion of the relative reactivity of these components of ROG once it has been determined in future research. VOC – Volatile Organic Compounds . In this report, “VOC” is used to indicate the total of all volatile organic gas from which ROG is the sub-set of gasses that are considered precursors of ozone. Zero air – Bottled, compressed gas made up of 80% N 2 and 20% O 2 . It is the flush gas for the flux chamber method that elimi nates contamination of an air sample by ambient air above the surface being sampled.

vii

### Abstract

Dairy operations in California were assum ed in 2004 to be major sources of Reactive Organic Gas (ROG) and therefore, ozone formati on in the Central Valley. In 2005 this project was proposed to determine the spec ific sources and components of ROG in emissions from dairies. An advisory gr oup of public agency, industry and academic members was formed to develop the initial plan and supervise revisions in accordance with initial results. Six dairies were sele cted to be sampled three times each year to evaluate facility and seasonal differences. Ambi ent air samples were collected initially to identify specific ROG components and dev elop analytical methods for dairy air samples. The initial data indicated t he predominance of alcohols in feed components of dairy ROG emissions and a sampling pr ogram was designed to focus on those while also monitoring other dairy ROG sources. The sampling program was conducted by Dr. Charles Krauter at CS U Fresno. The corresponding analytical program was administered by Dr. Donald Blake at UC Irvine. After review of the initial data, in 2006, the advisory group revised the sampling program to reflect the discovery that alcohols from the feeding operations, rather than manure management appeared to be the most significant ROG source. The six dairies were sampled three times from June, 2007 through July, 2008. T he highest flux rates were for silage and feed with an average flux rate of 4,229 μ g/m 2 /minute from the vertic al silage pile face and 19,170 μ g/m 2 /minute for loose, disturbed silage used for mixing feed. Fluxes from feed were 15,022 μ g/m 2 /min when first placed in the feed bunker, though the rate decreased to 2,929 μ g/m 2 /min as it was consumed. Fl ux rates for the flush lanes were considerably lower with a rate of 353 μ g/m 2 /min prior to the flushing operation that decreased further to 21 μ g/m 2 /min after the flush. O pen lots and exercise corrals were similar to the flush lanes. Areas of the corrals where the manure pack was relatively deep had flux rates of 243 μ g/m 2 /min. while the shallow manure pack in the open lots averaged 102 μ g/m 2 /min. The anticipated seasonal effects appear to be less significant than expected. Only em issions from the open lots correlate with surface temperatures, increasing in the summer and declining in winter. When the areas represented by each of these operations were applied to the flux values, it became apparent that feed was the dominant (60%) RO G source, followed by the open lots (25%), flush lanes (8%) and sil age piles (7%). These proportions were calculated as an example of a fictitious dairy that was a composite of the six sampled facilities. These percentages would vary when calculated from actual fluxes and facility dimensions but feed would probably re main the dominant source of ROG.

After this California Air Resources Boar d (CARB) supported project began, several related projects were added to the sampling program at the six dairies. Additional sampling and analytical systems were added as well as the collection of data related to nitrogen compounds, lagoon emissions, land application emissions, silage, feed, manure, soil and compost materials. These rela ted projects are still in progress. Only data related to the CARB contract is co mplete and reported her e. A comprehensive report of all projects related to sampli ng at these six dairies and other sites will be prepared at the end of 2009.

viii

### Executive Summary

Background In 2002, a study group made up of members fr om state agencies, academic institutions and the diary industry was formed by the Ca lifornia Air Resources Board (CARB) and the California Department of Food and Agricu lture (CDFA). This group was known as the Dairy Sub-Committee. T heir primary goal was to eval uate existing research to estimate the impact of dairy operations on ai r quality in California . In 2004, the San Joaquin Valley Air Pollution C ontrol District (SJVAPCD) began the process of permitting dairies in their jurisdiction. Many of t he Dairy Sub-Committee members became part of the Dairy Permitting Advisory Group (DPAG ) of the SJVAPCD. The primary issue addressed by the DPAG process was the uncer tainty regarding dairy emissions of the ozone precursors known as Reactive Organic Gas (ROG). ROG was defined as those Volatile Organic Compounds (VOC) that are ac tive in the atmospheric reaction that forms ozone. The Dairy Sub-Committee, noting the lack of current research in California related to this issue, advocat ed funding and solicitati on of proposals to address the problem. This project is one of the responses to that advocacy. The project proposal mandated an advisory group of industry, public agency and research representatives to oversee the study and suggest changes to increase the relevance of the project. The Dairy Sub-committee rema ined in that role throughout the project.

Methods The original, primary objective of this st udy was to evaluate the potential emission reductions from various methods for handlin g and managing dairy manur e. During the initial year, however, research by Dr. Frank Mitloehner at UC Davis suggested ROG emissions from feeding operations were more significant than thos e from the manure management processes. This was confirmed by the first flux chamber sampling by CSU Fresno and subsequent analysis by Dr. Bl ake at UC Irvine. The advisory group reviewed the initial data and recommended revi sions to the sampling program. The focus was shifted from ambient samples and dispersion mode ling of the whole dairy to more site-specific, flux chamber sampling methods that concentrated on feed and the feeding operations. Flush-lanes, corrals , lagoons and alternative manure management operations continued to be monitored and pr oved, as suggested by the UCD research, to have significantly lower R OG flux rates compared to the feed and feeding operations.

This CARB funded project was th e initial support for what became a much larger study with additional objectives beyond the moni toring of ROG emissions from dairy operations. The additional funding allowed ex pansion of the regular sampling program from five to six dairies. The focus on R OG by the project advis ory group was at the expense of the ammonia, methane and other air quality issues that were included as possible constituents to be sampled in the original proposal. These added, related projects include these other constituents along with more ROG monitoring of additional sources. The initial CARB funding is the onl y part of the study that has reached the end of its term. Most of the additional projects will be completed in 2009. Consequently, only the data and conclusions from this firs t ROG study can be reported here. Some supporting data from the other projects will be included as it applies to the CARB

ixx project. A comprehensive report will be prepar ed upon the completion of the related projects that will include t he data and results from this project compiled with the additional data from the other studies. T hat final report will be co mpleted in 2009.

Results Results from this CARB funded project are pr imarily from the flux chamber monitoring program developed and conduct ed by CSU Fresno to provide the analytical program at UC Irvine with air samples. The result s of the UCI analysis were correlated with site data to meet the primary objective of characterizing t he ROG flux rates from dairy operations and evaluating the variability of those fluxes. Total ROG flux rates were highest for silage. Undisturbed sil age had a flux rate average of 4,229 μ g/m 2 /minute. The disturbed silage pulled from the pile had an even higher rate, averaging 19,170 μ g/m 2 /min. The composition of these ROG fluxes was about 85% alcohols, predominantly ethanol. Feed mixed and deliver ed to the animals produced similar results. Immediately after placement in the feed bunkers, the flux rate averaged 15,022 μ g/m 2 /min but decreased to 2,929 μ g/m 2 /min over a period of 6 – 8 hours as it was consumed. Disturbing the feed by swee ping partially consumed material closer to the animal’s reach appeared to cause a sp ike in flux rate. ROG flux rates for manure management procedures were much lower than for feed. The flush-lane rates averaged 353 μ g/m 2 /min, prior to the flushing operation, and 21 μ g/m 2 /min after the flush. Open lot areas where manure not left in the flush lanes is deposited had flux rates that averaged 102 μ g/m 2 /min where the layer of manure was shallow and 243 μ g/m 2 /min for the deeper manure pack areas. Variability with respect to season was not apparent except for ROG fluxes fr om the open lots where there appears to be some correlation with surface temperature. No seasonal differences in the emissions from feed or flush lane operat ions can be shown with the data from this study.

Conclusions The monitoring procedures used in this pr oject produced calculated flux rates for a unit area of the process being sampled. While those values can show the ranking of the flux rates for the ROG sources, the calc ulated flux rate must be multiplied by the area at the dairy represented by the particular operation to determine its actual proportion of the facility’s ROG emissions. The areas of each source vary among the facilities as do the flux rates for each, as measured by this study. However, an estimate of the percentages that each of t hese four sources contributes to the total ROG emissions can be calculated from a composite of the six diaries sampled and the average flux rates from the study. W hen these flux rates are applied to the dimensions of the composite dairy, the highest flux rate fo r silage produces the lowest proportion (7%) of the dairy’s emissions. Flush lanes are 8%, open lots are 25% and feed is the major source at 60% of emissions. Differences in dairies and the variation in flux rates monitored in this study will produce different percentages for specific facilities but it is likely that the feed material will always be the major component of ROG emissions. Additional data from rela ted projects will be evaluated to include smaller emission sources such as lagoons and solids separation processes as well as better characterization of the va riability among different dairies.

### INTRODUCTION This project was conceived from the findings of two different st udy groups formed to evaluate air quality problems associated with dairy operations in California. The first of these groups was the Dairy Sub-committee organized in 2002 by the California Air Resources Board (CARB) and the Califor nia Department of Food and Agriculture (CDFA) and chaired by Dr. Matt Summers of CDFA. The sub-committee was made up of representatives from public agencie s (CDFA, CARB, USDA, EPA and SJVAPCD) academic researchers from UC Davis and CSU Fresno, and dairy industry organizations (Western United Dairymen, Da iry CARES, Hilmar Cheese and California Dairy Campaign). The primary goal of the Dairy Sub-committee was to evaluate existing air quality research related to di ary operations and recommend new projects needed by the agencies to develop science based r egulations. At the same time the Dairy Sub-committee was developing its reco mmendations, the San Joaquin Valley Air Pollution Control District was beginning to de velop a permitting process for dairies in their jurisdiction. A Dairy Permitting Advisory Group (DPAG) was formed and included most of the agency and industry members of the Dairy Sub-committe e. The primary issue addressed by DPAG was ozone formation and the role of dairy emissions in the level of ozone precursors known as Reac tive Organic Gas (ROG). ROG was defined as volatile organic compounds (V OC) that were reactive in the atmospheric production of ozone. In practice, ROG was all m easured VOC with the exclusion of methane, carbon monoxide, carbon dioxide and acetone. This project proposal was initially developed from the findings of the Dairy Sub-committee. As the DPAG process indicated the priority of ROG emissions, the or iginal, blanket proposal that also included ammonia, hydrogen sulfide and ot her air quality issues was revised by the Dairy Subcommittee to focus on R OG. The original proposal to CARB for this project mentioned those other constituents but the projec t advisory group mandated the emphasis on ROG sampling/analysis with the others relegated to monitori ng that could be done without interference with the ROG work. Additi onal funding from other sources became available over the course of the project to monitor these ot her constituents. That data will be reported in a later, more comprehensive report.

This CARB funded project was conduct ed over the past 36 months though the execution of six specific tasks, described below. Six dairies with different manure management practices and feeding procedures were evaluated over the course of the project. Nearly 600 ROG samples were collected and analyzed at UC Irvine for VOC species over the course of the project. CS U Fresno researchers, u nder the direction of Dr. Krauter, were responsible fo r the field work portion of t he project including collecting all samples, delivering samples to the IC Irvi ne laboratory, collecting relevant field data, and conducting additional field work to support the related projects. UC Irvine research group, under the direction of Dr. Blake, analyzed the sa mples for organic gases and assisted in the analysis and speciation of the collected emissions data.

The related projects, from the additiona l funding, will continue through 2009 and, in some cases, beyond to collect and analyze additional samples for alcohols, N compounds, silage and feed emissions, al ternative lagoon emissions, compost emissions, and land application emissions. Da ta related to these additional projects

1from UCI analysis as well as interpretation, correlation and conclusions related to those issues cannot occur until t hose projects are completed.



### MATERIALS and METHODS

Objectives There was a primary and three secondary objectives in the original proposal, adopted by the Dairy sub-committee. These objectives and their subsequent revisions by the sub-committee in their role as the proj ect advisory group are described below.

Primary Objective: The primary objective as st ated in the project proposal was to monitor and model ROG flux rates at baseline dairies and dairies with alternative manure handling systems to evaluate the potent ial for emissions reduction. While that objective remained significant, contemporary re search at UC Davis by Dr. Frank Mitloehner found higher flux rates from feeding operations than the manure handling processes that were to be studi ed in this project. Dr. Mitloehner and other members of the advisor y group suggested at the end of the initial year that the focus be shifted to feed and feeding operations while continuing to monitor manure management practices. The air sa mples collected by CSU Fresno and analyzed by UC Irvine were used to calculat e flux rates from sources associated with both feeding and manur e handling operations. These flux rates are summarized in the results section and the individual samples are listed in Appendix A.

Secondary Objectives: 1. A secondary objective, as stated in the project proposal was to monitor and model ammonia emissions from the tested dairies to eval uate the effect of the alternative practices on ammonia em issions and to improve baseline emission estimates. The GC-MS analyt ical program at UC Irvine, funded by this CARB project, was not the most efficient or cost effective method for ammonia monitoring, particularly with the emphasis on the feed sources. The advisory group recommended the ammonia sampling and analysis be assigned to a related project with the Un iversity of New Hampshire (UNH) to preserve CARB budget resources fo r the ROG analysis at UCI. A photoacoustic gas analyzer was suggested by an advisory group member and was evaluated against the ammonia denuder method used by the CSU Fresno research group in a previous fertiliz er emissions study. The INNOVA analyzer proved to be equivalent in accuracy to the denuder method for ammonia and had the additional advantage of providing real-time results. The INNOVA subsequently proved to be a useful secondary method of analysis for alcohols and other gases in the related projects. This first related study, funded by Dr. William Sa las of UNH from his USDA CSREES grant, enabled INNOVA monitoring of ammonia and several other N compounds from additional sampling at the six regular dairy sites. Results

2from that study will be in cluded in the comprehensiv e report to be completed in 2009.

2. Another secondary objectiv e, as stated in the project proposal was to use the CARB project award to obtain matching funding from the California State University Agricultural Research Initia tive (CSU/ARI). The CSU-ARI funding is from a program that r equires initial support from an external source which can then be matched. No CSU-ARI support would have been available without this CARB funding. A CS U/ARI project was proposed in 2006 to expand the regular sampling si tes from five in the original proposal to six and add other sites to be monitored periodica lly. The addition of the feed sources was included in this and a subsequent CS U/ARI proposal that funded most of the additional equipment and staff required for those sources. These CSU/ARI projects are scheduled to be completed in 2009 and 2010.

3. The final, secondary objective, as stated in the project proposal was to provide additional data fr om these dairies to cooperating researchers conducting projects related to ammonia, methane, N 2 O, PM, and other factors related to dairy operations. The relevant portions of the budgets for these cooperating projects shared the comm on field sampling and other costs with the CARB project. In addition to Dr. Salas at UNH, related monitoring projects at these dairy sites were funded by UC Riverside, Dr. Mitloehner at UC Davis, Sustainable Conservation, Engineered Composting Services, and the California Dairy Campaign. This additional funding was also used as match for the CSU/ARI projects descri bed in objective 2. A considerable body of data is being developed by t hese related studies and part of each agreement is a commitment to share all information from all projects with all cooperating agencies. The complete data set will be made available on a website and the results included in t he comprehensive repor t at the end of 2009.

The objectives of the project were to be me t through the specific tasks, listed in the proposal and outlined below in their original form. Modifications and additions to each of the or iginal tasks, as revised by the project advisory group, are shown in italics below each task.

Task 1. Select at least five dairies to monito r in cooperation with ARB and district staff. Ensure selected dairies are representative of typical conditions and operations. The additional projects and funding enabled a sixth dairy to be added to those to be sampled on a regular basis for comparison of their different methods of feeding and manure management. The six dairies were chosen with the assistance of several members of the advisory group and the approval of the entire group prior to the beginning of the sampling program. A list and description of each dairy can be found below.

3Task 2. Determine and evaluate specific fi eld sampling procedures to accommodate the unique features at each dairy. Pr epare field test plan including quality assurance objectives and data handling protocols and sample custody. The initial year of field work was designed to evaluate alte rnative sampling methods as well as determine the initial speciation of the dairy ROG emissions. The discovery of the significant alcohol emissions from f eeding operations showed the value of this strategy. The downwind-upwind ambient samples proved to be unsuitable for separating emissions from discrete operatio ns. The substitution of flux chamber sampling proved to be a much more viable method. Task 3. Conduct initial field sampling at each dairy, analyze collected samples and model emissions. Provide summary of results for review by the advisory group. The regular sampling of six dairies began in early 2006 and continued through summer of 2007. Various sampling methods were te sted and refined. In the spring of 2007, a summary of the Year-1 results was prepar ed and discussed at a series of advisory group meeting. That Year-1 repor t is attached as Appendix B. Task 4. Adjust sampling and analytical proc edures based on results from the initial sampling periods at each dairy. Revise field test plan. After discussion of the Year-1 results, a re vised sampling plan wa s submitted to the advisory group. That Year-2 program inclu ded not only the CARB sampling but also the complete field program for all the related proj ects that involved monitoring at the six regular sites. That field plan is described in the following section and in Appendix B. Task 5. Continue sampling and modeling at each dairy in the second year using consistent procedures on a regular basis to determine the effect of climate, crop season and seasonal dairy pr actices on emissions. The Year-2 program was approved by t he advisory group in September, 2007 and was implemented in October, 2007. Most of the pr ocedures were included in the spring and summer sampling in 2007 as well and are included in the data where appropriate. The final sampling period for the six regular dairies was completed in July, 2008. Analysis of UC Irvine samples was comple ted and reported to CSU Fres no in November, 2008. Task 6. Compare emissions from each dairy oper ation in the second year of the project to begin to determine differences between potential mitigation practices related to dairy operations. Prepar e report on results. The analysis of the samples taken at the six dairies and analyzed at UCI in Year-2 have been converted from concentrations to unit surface fluxes and are reported in the results section. A great deal of additiona l flux chamber data will be added to the body of data reported here when the rela ted projects are completed. Correlations between calculated fluxes and other data will be more va lid at that time and will be included in the comprehensive report at the end of 2009. Task 7. If, as anticipated, co-funding is av ailable from CSU-Agri cultural Research Initiative or other sources, select additional sites and waste mitigation processes to continue the work star ted with the initia l ARB funding.

4Additional funding for relat ed field work and analysis at these six sites and others was secured from CSU/ARI, CEC through UC- Riverside, USDA-CSREES through UNH and UCD, California Dairy Campaign, Engineer ed Compost Systems and Sustainable Conservation. The data set for all these related projects will be available on a project website beginning in April, 2009. The data will be summarized in the comprehensive report to be prepared upon completion of most of the related projects in December, 2009.

Field Sampling Overview The original project field sampling plan, developed by the advisory group, relied on collection of ambient upwin d and downwind air samples to be analyzed at UCI. Dairy ROG emissions were to be quantified thr ough downwind-upwind measurements from ambient air sample concentration data co llected for the various lagoons, corrals, and other dairy emission sources to be eval uated under the project. Samples were collected in standard 6-liter ev acuated summa canisters outfitt ed with regulators to allow time-integrated samples to be collected. Upwi nd samples were collected at a height of 1 to 2 meters, and downwind samples taken at heights of 1, 2, 5, and 10 meters for dispersion modeling. Sampling periods were to be selected to ensure a high likelihood of consistent wind speed and di rection necessary for effective emission flux estimates using the Industrial Source Complex Short Term version 3 (ISC-STv3) steady state Gaussian plume model. Each dairy samplin g event was to include a minimum of two sampling periods per day for at least two days. Following sample collection, all canisters were to be immediately shipped to Dr. Blake at UC Irvine for sample analysis and quantification.

This original plan proved to be uns uitable for a variety of reasons: 1. Wind speed and direction parameters for the ISC model were never achieved in 12 sampling events and several other failed sampling attempts. 2. Excessive requirements for the limited amount of GC-MS analysis available in the budget for UC Irvine precluded more int ensive sampling at each facility. After the evaluation of the unsatisfactory ambient samp ling, a number of alternatives were considered and a Year-2 sampling program emphasizing flux chamber sampling was developed and appro ved by the advisory group.

Quality Assurance Objectives Under Task 2 of the project, all field sa mpling, data collection, analysis, and reporting will be designed within a comprehensive Qua lity Assurance/Quality Control (QA/QC) program. The objectives of the QA/QC program will ensure and document the precision, accuracy, completeness, repr esentativeness, and comparability of collected data.

The QA/QC procedures for the field sampling are included in the Year-2 plan, (Appendix B). The QA/QC program for the UCI analysis was included in the original proposal and is attached in Appendix C.

5Sample Coordination and Recording All samples were to be account ed for from the time of collect ion until results are verified and reported. Sample custody procedur es provide a mechanism for clearly documenting field records, sample labels, a sample master logbook, sample shipment and receipt chain-of-custody, sample hand ling procedures, and sample preservation protocols.

A series of field log sheets were develo ped, specific to each sampling operation. These sheets were designed to combine da ta for the ambient conditions, location details, sampling parameters and all other samp ling related to the specific location and date on a single, master sheet. Examples of these log sheets are shown in Appendix D. The primary use of these samp le logs will be to coordinat e the data from the UC Irvine analysis reported here with other data for the same locati ons related to the other projects for the comprehensive report.

Calibration Procedures and Frequency All sampling equipment, sampling canister cleaning equipment, laboratory analytical equipment, instrumentation, and other analytical devices was to be maintained and calibrated according to manufacturer’s specif ications. All key equ ipment was regularly calibrated to ensure full and accurate operati on. Calibration result s will be properly documented and retained. Detailed standard operating procedures for key processes will be provided as part of project reporting.

Calibration procedures for this CARB portion of the overall study are all related to the UC Irvine analytical procedures found in Appendi x C. Calibration of field analytical equipment and CSU Fresno procedures for the rela ted projects are detailed in the Year2 program in Appendix D.

Data Reduction, Validation, and Reporting All key project field, laboratory, and analysis data was to be stored in appropriate databases or spreadsheets for analysis and documentation. Blank sample analysis, QA analysis, out of range data analysis with qualifiers, and all other relevant data descriptors and qualifiers will be fully documented.

Analyses of the canister samples at UC Irvi ne were reported in proportional volumetric units, pptV (parts per trillion by Volume). Calc ulation of ROG flux from this data was a two step operation:

1. Each constituent in the UC Irvine data had to be converted from a volume proportion to a mass in order to accurately sum them for an ROG total. pptV X molecu lar weight X 0.0000409 = μ g/m 3
This formula gave a mass value for each constituent per unit volume of air so the sum of the gasses identified as R OG could be expressed as mass for the calculation of flux.

62. Each constituent and the sum, in μ g/m 3 of air, could then be converted to a flux rate by a formula described in the US-EPA Isol ation Flux Chamber methodology (Appendix D). The area covered by the par ticular flux chamber (0.1924 m 2

) and the rate of flow of the zero-air flushing gas (10 liters/minute = 0.01 m 3 /minute) were required for this calculation.

μ

g/m 3 X (0.1924 m 2 / 0.01 m 3 /minute) = flux rate μ g/m 2

/minute All flux rates in tables 3-10 in the results section as well as the individual samples shown in Appendix A were calculated in this manner.

The analytical results from UCI along wit h conversion steps from the reported concentrations to the flux values reported here will be available on a website to be set up as part of the comprehensive data set for the entire project. Th e data for the CARB study along with feed, silage, manure, soil and ambient conditions will be available to all participating agencies and researchers on th is project website by April, 2009. Additional data will be added to that website as it is devel oped. A final report of the comprehensive project will be pr epared at the end of 2009.

Sampling Sites The original proposal called for five dairi es to be selected for a regular sampling program over the term of t he project. The addition of t he related projects enabled the regular sampling program to be expanded to six dairies. The sa mpling periods were chosen by the advisory group to reflect thr ee different times during the season when both the climate and the operations at the diaries would be different from the other two sampling periods of th e Year-2 program.

The regular sampling periods were selected as: Winter = January – March Early Summer = May – July Fall = September – November

The dairies were originally selected to have different manure handling systems. As discussed above, ROG from the feeding operations was show n to be more significant and so the focus of the study was alter ed to emphasize feed and silage while still monitoring emissions from the manure m anagement systems. Fortunately, the six dairies were sufficiently different with re spect to silage, commodities, feeding schedule and feed management to be a repr esentative sample of feeding practices across the dairy industry. Characterization of t he feed and feeding practices involves more sampling and records with r egard to the materials and ration. Most of this characterization is still being done as par t of the continuing projects and will be documented in detail in the report at the end of 2009.

One of the first suggestions fr om the industry representatives in the advisory group was to preserve the privacy of the cooperating dairies. A pproximately a dozen dairymen were contacted and considered for the regular sampling program. Each was reluctant until anonymity was promised. Several quest ioned the ability of t he research group to

7maintain their privacy. Each cooperat ing dairy operation was given the following

assurance: 1. The name of the dairy would not appear in any reports or published documents related to the project. 2. The address or location of the dairy would not appear in any reports or publications beyond identifying all six as being in the San Joaquin Valley. 3. All records such as feed rations, lab reports and other docum ents obtained from the dairy for the purpose of supporting t he project would be redacted to remove identifying information. 4. Each dairy would be ident ified by a letter (A – F) 5. The published reports would state that the dairies we re located from Tulare County north to Stanislaus County. 6. Each dairy operator would be furnished with all data collected from that particular operation and would be given a draft of the final report to review prior to publishing. (This will apply to the final , comprehensive report to be published at completion of all related projects rather than this CARB report).

Dairy Descriptions The six dairies selected for the regular sampling, designated by letter, and their operational characteristics are these:

A. A free-stall, flush-lane dairy m ilking 2000 cows with 350 dry cows and 500 heifers. The manure is flushed into a pr ocessing pit, over a sloping screen and into one of two treatment lagoons. Effl uent flows from the treatment lagoon to a large storage lagoon where it is mi xed with fresh water and applied tosurrounding cropland. The separated solids are used for bedding in the freestalls. Lane flushing, corral scraping and other maintenance operations are more frequent than at the average dairy. The feed storage and mixing operations are carried out on site.

B. A 3000 cow dairy with 500 dry cows and no heifers. The manure is flushed into small pits at the end of the barns, pumped over a sloping screen and into a single large lagoon. The barns are a free-st all system with cow mats for bedding instead of composted manure. Effluent from the lagoon is pumped into the irrigation pipeline system where it mixes with irrigation water and is applied to surrounding cropland. Also, lagoon effluent is separated from solids via the liquid-solid separator. Corrals ar e scraped infrequently. Feed storage and mixing operations are done at another location approximately 1km from the site.
C. A free-stall, flush-lane dairy milking 525 cows with 150 dry cows and heifers. The manure is flushed into a small proce ssing pit, over a sloping screen and into a series of four treatment lagoons. The volume of th e lagoons is very large for the animal population and the or ganic loading of the lagoons is very low. Each lagoon has several circulators t hat operate continuously. The lagoon environment is such that photosynthetic microbes are prevalent, giving the lagoon a purple/red color. The effluent from the final lagoon in the series is used as irrigation on 130 acres of pasture for the dry cows and heifers and is also

8delivered to a neighboring farm for producti on of forage and other crops. The feed storage and mixing operations are carried out on site.

D. A free-stall, flush-lane dairy milking 3700 cows with no dry cows or heifers on site. The manure is flushed into a large processing pit, over a series of sloping screens, through two treatment lagoons and fi nally into a large storage lagoon. The lagoon system is doubled so that half the effl uent from the separation screens is processed in each of two series of treatment lagoons. Both sets of treatment lagoons feed into the large storage lagoon. All treatment lagoons and the storage lagoon have several circulat ors that run continuously. The separated solids are used for bedding in the fr ee-stalls. The effluent from the storage lagoon is pumped onto cropland when needed for fertilization of the 880 acres of forage. A nutrient management consultant monitors the soil, crop and lagoon effluent to determine the optimum use of effluent for crop nutrition and to avoid N leaching problems. The feed st orage and mixing operations are carried out on site.

E. A free-stall dairy that utilizes a vacuum truck to collect the undiluted manure slurry from lanes twice each day. The dairy milks 1000 cows with 200 dry cows and heifers. The manure slurry is pumped fr om the truck to a plug-flow digester with a residence time of approximately 21 days. The gas from the digester is used to power a 100 kW generator. Effl uent and solids from the digester are separated using a screw press with t he solids used for beddi ng and the liquid stored in a lagoon for us e on surrounding orchards and cropland. In 2007, the free-stall beds were converted to cow mats as opposed to composted manure beds. The feed storage and mixing operatio ns are carried out on site.

F. A free-stall dairy with lanes similar to a flush-l ane system. The dairy milks 2500cows with no dry cows and no heifers on site. The cows are kept in the freestalls with very small open lots. This dai ry utilizes water mattresses in the freestall barn as opposed to composted manur e bedding. The lanes are not flushed as is the usual practice in similar oper ations. Undiluted manure slurry in the lanes is scraped into small pits at the c enter and end of the free- stall barns. The slurry then drains to large holding pits in between the free-stall barns without being flushed with a large volume of wate r. The dairy is surrounded by extensive cropland. The manure slurry from the st orage pit is pumped into a large tanktrailer, hauled to a field and the slurry is injected 20cm below the surface of the soil. The feed storage and mixing oper ations are carried out on site.

Regular Sampling Program (Year-2) Tasks 2 and 3 of the proposal established the first year’s (Year-1) sampling program once the six dairies were selected. That progr am was primarily to co llect initial data for speciation of dairy ROG and to evaluate va rious sampling and analytical methods to be validated and used in the final year (Year-2) of the study. A Year-1 report was prepared in the spring of 2007 and submitted to CARB in July. That report is attached as Appendix B. Prior to subm ission, a draft was provided to the advisory group for discussion of the changes in the sampling progr am for Year-2 as required for Task 4.

9After several meetings, the following modifi ed sampling program was approved by the advisory group and implemented for t he fall, 2007 sampli ng period.

Note: This plan includes all sampling for a ll related projects. Only samples designated “UC Irvine” pertain to this CARB project and the data reported below. Data from the other sources listed will be added to the CA RB/UC Irvine data in the comprehensive report at the end of 2009.

The Year-2 monitoring plan proposed in the Annual Report subm itted to the ARB Research Division in May, 2007 was modified after discussions with the ARB staff, the local air district staff and the advisory group at the July 12, 2007 meeting. After input from the advisory group and furt her discussions with the ARB staff, several changes to the original monitoring plan were adopted. T here were three signif icant areas where the plan was modified:
1. The ambient sampling that requires s pecific wind conditions and consumes at least six canisters and subsequent GC -MS analysis at both UC Irvine and CSU Fresno was eliminated from the regular sampling program. It was found to be impossible to obtain the required wind cond itions at each dairy for each of the sampling periods. Under the best conditions, this monitoring/modeling only differentiates between emissions fr om animal housing vs. lagoons. These results, from uncertain modeling c onditions, consumed nearly half of the canisters and analytical activity for resu lts of limited value. The unexpectedly significant emissions of alcohols from feed and fresh manure (see item 2 below) will require additional canisters and GC-MS analysis for documentation. The elimination of the regular ambient sampling will enable the re-direction of those resources to the more critical feed and silage monitoring. Ambient downwindupwind sampling will be added, when wind c onditions warrant, to the special sampling program discussed below in item 3.

2. The most significant new information fr om the Year-1 data is the documentation of significant emissions of alcohols, par ticularly from feed and silage but also from fresh manure. In so me instances, the two dominant alcohols, ethanol and methanol, comprise well over 90% of t he total monitored ROG emissions. The original monitoring plan did not include sufficient sampling to adequately document the emissions from those sour ces, particularly with regard to their spatial and temporal variability. Afte r discussion in the Dairy Sub-committee and consultation with the ARB staff, the fo cus of the sampling plan has been shifted to these sources of alcohols. Additi onal canisters and analysis at UCI and CSU Fresno will be devoted to silage and Total Mixed Ration.

3. The regular monitoring of the six dairies as described in the original proposal will be supplemented by additional samp ling between the scheduled sampling periods. More intensive sampling of al cohol sources to better characterize variability, additional feed compo nents and ambient sampling when wind conditions are suitable will be done on two of the six dairies as the opportunities

10are presented. Additional monitori ng of emissions from lagoons and land applications of lagoon effluent will also be done when possible, primarily for N compounds but the full suite of R OG’s will also be monitored.

The modified Year-2 monitoring program for t he regular sampling of the six dairies is shown in Table 1 and the special sampling progr am is shown in Table 2. These were approved by the CARB staff and the projec t advisory group for t he monitoring period scheduled for September/October, 2007, co ntinued through January/February, 2008 and May/July, 2008.

Table 1 . Modified Year-2 monitoring program adopted for Fall-07. This monitoring program, after approval by ARB and the pr oject advisory group was used at the six dairies for the regular sampling and analys is from September/October, 2007, through January/February, 2008 and May/June, 2008.
CSUF Dairy Flux Chamber Sampling Sources and Analytical Methods- Year 2
Proposed Sampling Program at Each Da iry- Routine Sampling (6 Dairies) (Number of Samples)

Source Locati

on # Analytical Method Additional Tests

Innova 1412 UCI Can CSUF Can TO-17 Tube Lab Samples Silage Density Silage Aerobic Stability Feed Sources

Total Mixed Ration (0.5 h Post Placement- Not Consumed) 1 & 2 2 1 1 1 2 - -

Total Mixed Ration (~6 h Post Placement- Consumed) 3 & 4 2 1 1 1 2 - -

Total Mixed Ration (~6 h Post Placement- Not Consumed) 5 & 6 2 1 1 1 2 - -

Silage Pile Disturbed Face 7 & 8 2 1 1 1 2 - - Silage Pile Vertical Undisturbed Face 9 & 10 2 1 1 1 2 4 2

Field Blank 11 1 1 1 1 - - - Media Blank - 1 1 1 - - - - Total Feed Sources (Each Dairy) 12 7 7 6 10 4 2
TOTAL Feed Sources (6 Dairies) 72 42 42 36 60 24 12
Manure Sources

Open Lot/Corral (Deep Manure Pack) 1 & 2 2 1 1 1 2 - - Open Lot/Corral (Shallow Manure Pack) 3 & 4 2 1 1 1 2 - -

Flush Lane (Pre-Flush) 5 & 6 2 1 1 1 2 - - Flush Lane (Post-Flush) 7 & 8 2 - 1 - 2 - - Bedding 9 & 10 2 - 1 - 2 - -
Field Blank 11 1 1 1 1 - - -
Media Blank - 1 1 1 - - - - Total Manure Sources (Each Dairy) 12 5 7 4 10 0 0
TOTAL Manure Sources (6 Dairies) 72 30 42 24 60 0 0 Total Feed & Manure Sources (Each Dairy) 24 12 14 10 20 4 2 TOTAL Feed & Manure Sources (6 Dairies) 144 72 84 60 120 24 12

11Table 2 . Special Sampling program proposed for Year-2. This monitoring program was conducted at two of the six dairies between the scheduled sa mpling periods. Most of this activity was conducted for the related projects but the UCI data is shown in the Results section of this report.

CSU Fresno Dairy Flux Chamber Sampling Sources and Analytical Methods- Year 2

Proposed Sampling Program at 2 Dairies- Special Sampling (Number of Samples)

Feed Source Analytical Method Additional Tests

Innova 1412 UCI Can CSUF Can TO-17 Tube Lab Samples Silage Density Silage Aerobic Stability Silage Pile

Silage Pile Disturbed Face 2 2 2 1 2 - - Silage Pile Vertical Undisturbed Face 2 2 2 1 2 4 2
Main Commodities

1- 2 1 1 1 1 - - 2- 2 1 1 1 1 - - 3- 2 1 1 1 1 - - Total Mixed Ration (TMR)

TMR +0.5 h Post Placement (Not Consumed) 2 2 2 1 - - -

TMR +1.0 h Post Placement (Consumed) 2 2 2 1 - - - TMR +2.0 h Post Placement (Consumed) 2 2 2 1 - - - TMR +3.0 h Post Placement (Consumed) 2 2 2 1 - - - TMR +4.0 h Post Placement (Consumed) 2 2 2 1 - - - TMR +5.0 h Post Placement (Consumed) 2 2 2 1 - - - TMR +6.0 h Post Placement (Consumed) 2 2 2 1 - - - Total (Each Dairy) 24 21 21 12 7 4 2 TOTAL (2 Dairies) 48 42 42 24 14 8 4

In addition to comments and suggestions fr om the advisory group that generated the modified programs described abov e, there were a number of questions related to the documentation of the sampli ng and the dairy operations. A summary of the flux chamber procedures as applied to the sampling locations at these dairies follows this section. These photos and descriptions il lustrate the application of the US-EPA Isolation Flux Chamber methodol ogy to these specific monito ring sites. More detailed descriptions of the flux cham ber methodology as well as exam ples of the forms used to document the sampling locations are attached as Appendix D.

12Figure 1. Flux chamber sampling of an open lot ar ea at Dairy B. T he canister sampling the chamber on the left was analyzed by GC /MS for data reported below. The gas analyzer in the cart and the ammonia denuder on the top of the chamber on the right are sampling for data to be included later in the comprehensive report.

The flux chamber is placed on the surface to be monitored with care to disturb the surface material as little as possible. A tight seal is not required because of the continuous flow (10 L/minute) of sweep air into the chamber, resulting in a positive flow out of the chamber through bot h 1 cm vents in the top and gaps at the bottom of the chamber. The sweep air is commerci ally available “zero-air” (80% N 2 plus 20% O 2 ) in the cylinder at the center of Figure 1. The chamber is flushed for 30 minutes prior to any sampling to eliminate ambient air tr apped as the chamber was placed on the surface. After the 30 minute conditioning period, various samples can be taken for another 30 minutes before significant changes in the surface conditions could occur due to the enclosed atmosphere. Initial tem perature measurements ar e recorded for the ambient air and surface as well as the air an d surface inside the chamber. The ambient and chamber temperatures are recorded again at the time of sampling. Flux sampling of the open lots was done in this manner; fo llowed by manure/soil samples collected where the chambers were placed.

13Figure 2. Flux chambers during the conditioning period prior to sampling on a flush lane at Dairy B.

Sampling of the flush lanes began when the cows were feeding and ruminating prior to flushing so that the manure/ur ine slurry was relatively thick in the lane as shown in Figure 2. The one-hour monitoring period was tim ed to occur just prio r to a flush so the exclusion of the cows from the sampling area would not reduce the am ount of manure to be sampled below what w ould normally be found there in the 3 hours prior to the flush. Once the Pre-Flush samples were collected, the lane was flushed and the chambers were set up at the same location. That often coincided with the cows being milked so the barn was empt y and no manure was deposited in the lane during the onehour sampling period. The flushing cycles were from 6 to 12 hours apart so it appeared this monitoring program was appropriate to determine the beginning and ending conditions of the cycle. Deposition of m anure was continuous once the cows returned from milking so an average of the Pre-flush and Post-flush emissions should give a reasonably accurate picture of the flus h lane emissions during the cycle.

14Figure 3. Flux chambers sampling Total Mix ed Ration at Dairy A. This is an intermediate sample, a few hours after placem ent of the feed, as shown by the absence of nearly half of the TMR and the distur bed top of the pile of feed.

Monitoring the TMR with the flux chambers required considerable care and method development. The feed is delivered from a la rge truck or wagon 2 – 4 times each day. It was apparent from the init ial sampling that the TMR was both a significant and variable source. Chambers were placed on t he TMR just after it was delivered to the bunker. The conditioning period for the ch ambers precluded any sampling prior to 30 minutes post-placement so this first sample is considered the initial value. It was apparent that the emission rate decreas ed as the TMR was both consumed and exposed to the air over the period of about 6 hours that it was in the bunker. Sampling for UCI analysis took place at the beginning and on the residue remaining after 6 hours. Sampling was also done on the surface of the bunker after the TMR had been consumed or swept up prior to the subsequent f eeding operation. Some TMR sampling was done between 30 minutes and 6 hours for the special sampling to be reported in the comprehensive report. Portions of that intermediate data are shown in Figures 6 and 7 to illustrate the decrease in em issions over time from the TMR.

15Figure 4 . Flux chamber sampling of silage at Da iry C. Initial sampling of “disturbed” silage pulled down from the pile, shown by the two chambers on the right of the photo, indicated very high emissions of alcohols from that source, under these conditions. Sampling the relatively larger surface of the “undisturbed” silage of the pile face required a frame to hold the chamber agains t the vertical face shown by the two chambers on the left. Canisters for GC/M S analysis are on the ground at the rightcenter, near the Zero-air cylinder and flux chambers on the small pile of disturbed silage.

Silage as described in the results section below needed to be monito red in two forms. The compacted, vertical face of the silage pile was very dense and required the chambers to be held against the surface by a rack constructed for that purpose. There was also an amount of silage pulled loose fr om the face by the equipment used to mix the TMR. That distur bed silage had a lower density and appeared to be more biologically active. Chambers could be placed on this loose silage at the base of the pile face to determine the differences in em ission rates from the two forms of silage. Core samples were taken from the face at the location of the undisturbed samples and analyzed for composition and density.

16Figure 5. Flux chamber field blank at Dairy F. The flux chamber is placed on a clean, Teflon sheet on the floor of the equipment tr ailer; then conditioned and sampled by the same procedures used to collect samples fr om dairy sources. Here the chamber is being conditioned to determine a field blank i mmediately after sampling TMR at Dairy F.

A field blank was collected at least once each day, following the sampling procedures described above. A Teflon sheet was cleaned with distilled water, wiped dry and placed on the bed of the truck or equi pment trailer while parked in the location of the most recent sampling procedure. The chamber was conditioned with sweep air and then sampled by a UCI canister as well as t he other methods used for that day’s data collection. In addition to the field blanks, a media blank was also prepared by filling the canister with the zero-air used for sweepi ng the chamber and sent to the lab for analysis. The media blanks were prepared at the same time the field blanks were collected. Field blank and media blank data c an be found on the project website. Data reported in Tables 2 – 10 of this repor t have been corrected by subtraction of the appropriate blank.

17

### RESULTS

Over the period from June, 2006 through the end of the regular sampling period in July, 2008, a total of 556 air samples were collect ed in 2 liter canisters and analyzed by Dr. Donald Blake at UC Irvine. The first 57 of these were ambient air samples to be used for speciation of dairy ROG emissions and eventually downwind-upwind differences for dispersion modeling. These ambient sa mples were successful in confirming the contemporary research at UC Davis showing the predominance of alcohols, particularly ethanol, in dairy emissions. Modeling downwi nd-upwind samples to calculate flux rates requires consistent wind direction and a minimum wind speed of 1 m/sec. The consistent wind direction could sometime s be obtained with some difficulty but the consistent minimum wind speed was never achieved in 12 attempts.

The advisory group’s recommendation to focus on feeding operations required a method of monitoring that was more spec ific than downwind-up wind sampling could provide, even with appropriate wind conditi ons. The EPA Isolation Flux Chamber method (described in Appendi x D) proved to be much more suitable in obtaining emission fluxes for specific locations and su rfaces at the dairies . A number of flux chamber samples were collected in Year-1 and summarized for the advisory group in April, 2007. After comparing the flux cham ber results with the unsatisfactory downwindupwind data, the advisory committee decided to change the major sampli ng effort to flux chamber measurements and in crease the emphasis on operations related to feeding while still monitoring manure management in Year-2.

In the Year-2 program, the sampling for the CARB portion of the project is designated as the UCI Can samples in Table 1. A mo re detailed evaluation of feed and silage also used UCI Can samples to study silage vari ability and the feeding operation in more detail. The special sampling is described in Table 2 and the data from the UCI Can samples is reported below. Comprehensive evaluation will not be possible until the completion of related projects later in 2009.

The regular sampling program, designated as the Year-2 program, began in the fall of 2007 and was completed in summer of 2008. The UC Irvine/CARB portion of that program included 78 samples from silage, 144 sa mples of feed (TMR), 91 samples from flush lanes, 64 samples from open lots or co rrals, and 102 samples for field and media blanks. Results reported below, with the exc eption of the ambient samples in Appendix A, Table A6 are corrected by the subtraction of an appropriate field blank for that day. Some samples taken prior to the beginni ng of the Year-2 program did not have UC Irvine field blanks for corrections and are not reported here. Data from the related projects may provide adequate QC for these samples so they can be reported later.

The average flux rates for each of the four dairy operations that made up the regular sampling program during the Year-2 peri od of summer, 2007 through summer, 2008 are shown in Tables 3 through 8 and summarized in Table 10. These are the average flux rates for all dairies and dates. Table 10 in dicates the relative differences among the four dairy sources of feed, the Total Mi xed Ration, flush lanes and open lots. The

18individual analyses averaged for the tables in this section are shown in Appendix A. While each sample taken was analyzed for a ll identified gasses by UC Irvine, most samples included only a few components in significant quantities. The alcohols mentioned above made up the major portion of near ly all samples from each operation. A few others such as acetaldehyde, di-methyl sulfide, (DMS) and di-methyl-disulfide were sometimes as much as 1% - 15% of some samples. Two of the dairies (A and D) included cull citrus pulp in t heir TMR with the result that significant amounts of limonene were found in their TMR and manure samples. In order to reduce complexity in the tables, only the significant components of th e fluxes, the alcohols, acetaldehyde, DMS and limonene are shown in the results t ables. The remaining ROG components analyzed by UC Irvine were nearly always in trace concentrations, at most and contributed less than 1% to the total ROG flux. The complete analysis of each UC Irvine sample including the trace components will be reported on the pr oject website.

Silage Flux Rates The highest flux rates monitored in the st udy were from the co mpressed and fermented forage known as silage. Silage is generally the largest component of the Total Mixed Ration that is made up at the dairy and fed to the animals. It is 40% - 65% of the TMR and provides both energy and nutrition. Silage is most often made from corn grown near the dairy. It is harvested in early fall by chopping the entire plant just as it reaches maturity. The chopped plant material is pile d at the dairy, compacted and covered. The material ferments and, if compacted sufficiently, the interior of the pile will be anaerobic to the point that lactic ac id fermentation will lower the pH until no further microbial activity can occur. In this form the sil age can be stored for severa l months to provide feed for the cows through the winter and spring when their energy and nutrition requirements are highest.

The silage emissions monitored in this study were from both the compressed, undisturbed silage at the “face” of the covere d pile, Table 4, and the loose silage pulled down from the face to be used for making up the next TMR to be fed. The disturbed silage data is shown in Table 3. The flux ra tes for disturbed material are higher than the undisturbed silage piles by a factor of 5. This is most likely due to the rapid fermentation and other microbial activi ty that would be stimulated when the compressed, anaerobic material is pulled lo ose and exposed to air. The very high percentage of ethanol from ferme ntation may be an indication that this is occurring. The variability seen in emissions fr om disturbed material, compar ed to the more consistent emissions from the undisturbed silage in Table 4 is an indication of differences in both silage composition and quality. A less com pacted silage pile will be less anaerobic and may degenerate more rapidly when exposed to ai r. This variability will occur in both disturbed and undisturbed silage but is likely to most prevalent when the material is aerated by the feeding equipment. The high le vels of DMS are possibly indications of spoilage related to high protein silage. Ammonia and other N compound emissions as well as silage composition and density were monitored for a related study and those results should provide considerably more det ailed evaluation of silage quality vs. flux rates in the later report.

19There is considerable variation among the si x dairies with regard to silage flux rates shown in Tables 3 and 4. Corn silage is most common but dairies B and F also made silage from small grains such as wheat and bar ley. This “winter silage” has a different protein and energy content and would produce different emissions of alcohol and other constituents. It is also a mo re coarse material and more di fficult to compress so it may degrade more rapidly. Emissions from the diffe rent types of silage will be separated in more detail when the data from the relat ed projects is complete and reported.

Potential for emission reductions relat ed to silage management might include minimizing the disturbance of the silage by on ly pulling sufficient mate rial from the pile to make up the current feed mi x. In spite of the high flux rates from silage, it is a relatively small area compared to the rest of the dairy and complicated changes in silage management may not have as much potential to contribute to the overall emissions of ROG from a dairy.

Table 3 . Average flux rates for “disturbed silage” material pulled loose from the pile face for use in the next mixed ration. Individual data averaged for this table can be found in Appendix A, Table A1. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Dairy Averages Surface Air A 25.7 22.5 19,018 13,001 1,383 14,407 80% 480 287 1 3,776
B 22.1 15.4 2,961 2,558 325 2,892 98% 32 3 1 34
C 24.6 18.8 36,192 34,828 555 35,401 93% 303 9 1 451
D 27.5 20.5 18,620 8,810 459 9,283 84% 41 4 2 9,266
E 27.1 18.4 13,789 10,440 555 11,004 78% 76 1 1 2,636
F 19.4 19.5 20,252 7,111 513 7,637 75% 321 0 1 12,287 Ambient Temperature (degrees C)

20Table 4. Average flux rates for “undisturbed s ilage” material still compacted in the exposed face of the pile. Individual data averaged for this table can be found in Appendix A, Table A2. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Dairy Averages Surface Air
A 27.0 21.4 4,848 3,575 573 4,167 88% 192 11 1 471
B 22.2 17.5 5,577 4,540 282 4,823 86% 16 1 1 738
C 23.8 17.2 5,368 3,605 496 4,107 79% 152 5 1 1,095
D 26.2 16.7 6,124 4,439 697 5,198 85% 665 18 0 239
E 21.5 16.8 2,636 1,798 294 2,094 84% 24 2 0 513
F 19.9 20.7 1,905 1,542 203 1,745 91% 53 0 1 106 Ambient Temperature (degrees C)

Total Mixed Ration and Feed Materials Flux Rates The general term for the ma terial fed to the dairy herd is “Total Mixed Ration” referred to here as TMR. The TMR is usually made up from components at the dairy though some may truck it in from another facility as is done at Dairy B. The TMR is mixed from silage and alfalfa hay with various commodities su ch as distiller’s grain from ethanol production, cotton seed meal, almond hulls and other commodities that can provide energy and nutrition. Most dairies employ a consulting nutritionist to recommend the most economical components available to provide the energy and nutrition needed for the cows. The TMR is mixed and fed generally twice each day in a bunker or trough so the cows can eat when they choose. TMR is usually consumed in 6-8 hours. Dairies scrape or sweep the remaining feed after about 5 hours so the cows can reach it more easily from the flush lane. This practice ma y affect ROG emissions as seen in the data below.

ROG emissions were monitored by flux ch ambers on the TMR immediately after it was placed in the bunker. The flux chamber procedure requires 30 minutes before sampling can take place (see Appendix D) so the flux rates could not be measured until that time. As the cows consumed t he feed, the amount decreas ed and the TMR appeared to change as it dried. As was observed with s ilage, disturbing the material appeared to stimulate emission of ROG. The mixing and delivery of TMR with its large percentage of silage would be expected to produce a sp ike of emissions. The advisory committee anticipated this and included further sampling of the TMR at 6 hours post-placement for the Year-2 program. When possibl e, a sample was taken of the bunker surface after the TMR was completely consumed. This was often done 6 hours post placement when most of the dairies would sweep the remain ing TMR to a small p ile nearer the flush lane. The 6 hour TMR sample and the “6 hour consumed” sample could be taken simultaneously.

21The Year-2 TMR flux rates fo r the post-placement time per iods are shown in Table 5 and the averages for each dairy monitored are in Table 6. The magnitude and variability of TMR flux rates ar e the most significant features of these tables. The rates are highest just after feed placement as anti cipated and show a significant decrease at 1.5 hours. The flux rates at 6 hours incr ease to about twice the level at 1.5 hours though the bunker surface when the feed is c onsumed is decreased. The increase in ROG flux rates at 6 hours occurred primarily at Dairies A, B, C, and D while Dairies E and F show a continuing reduction in emissions ov er time (see Table A3 in Appendix A). Those first four dairies scrape and sweep t he TMR more frequently and it may be that disturbing the feed stimulates ROG emissi ons as it appears to do with silage.

The special sampling described in the Yea r-2 program added more frequent monitoring of TMR at Dairies A and B in addition to the regular sa mpling reported here. Flux chambers were used to continuously monito r the feed from plac ement until it was consumed. Data from the special sampling of this related project will be included in the comprehensive report and should better char acterize the relationship between TMR management and flux rate. Some UC Irvine sa mples and analysis was included in this special sampling program. While the related project is not yet co mpleted, the UC Irvine analysis is finished and the results of five monitoring periods are graphed in Figure 6 for total ROG and Figure 7 for alcohols. The comprehensive report wil l include this data along with other sampling and supporting in formation to better characterized the changes in TMR fluxes with time.

Table 5 . Average TMR flux rates for all dairies sampled compared to elapsed time from placement in the feed bunker. The 1.5 hour values were only taken in spring, 2007 and do not correspond to all of the 0.5 and 6 hour post-placement values. The 6 hour postplacement values may, in many cases in clude sweeping or scraping of the TMR about 4-6 hours after placement, the 1.5 hour samp les do not. Values labeled “consumed” are the feed bunker surface after the TMR wa s consumed. Individual data averaged for this table can be found in Appendi x A, Table A3. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Total Mixed Ration (0.5 h Post Placement) 15,022 11,668 1,460 13,141 86% 336 584 26 831 Total Mixed Ration (6 h Post Placement) 10,582 7,747 1,591 9,350 87% 469 557 9 152 Total Mixed Ration (6+h Post: consumed) 2,929 2,289 389 2,683 89% 106 102 3 32

Total Mixed Ration (1.5 h Post Placement)* 4,507 3,394 547 3,941 90% 15 459 34 12 *sampled spring, 2007 only- see comments in text

22Table 6 . Average TMR flux rates for each dairy sampled. Values are averages of all samples taken over the feeding period w hen TMR was present. Individual data averaged for this table can be found in Ap pendix A, Table A3 . Values are in
μ g/m 2 /minute and are corrected by the subt raction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Dairy Surface Air A 13.9 13.7 9,674 5,356 2,074 7,440 76% 275 1,772 12 85
B 19.9 18.7 7,445 5,127 1,257 6,391 90% 304 2 28 679 C 24.0 17.1 15,549 14,376 602 14,983 95% 314 26 6 187 D 22.9 20.2 10,487 8,165 1,078 9,256 87% 326 641 8 169 E 19.4 20.1 5,781 4,778 432 5,214 90% 142 2 20 368 F 21.1 22.7 3,383 2,591 550 3,150 93% 103 1 27 96 Ambient Temperature (degrees C)

Total ROG Emission Rates from TMR

0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000

012345678

Hours after TMR PlacementROG flux (μg/m2/min)

9

A 2/11/08 A 5/28/08 B 11/20/07 B 2/27/08 B 6/30/08

Figure 6. Total ROG fluxes relat ed to time after feed plac ement from additional TMR flux data sampled as part of a related project.

23Total Alcohol Emission Rates from TMR

0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000

012345678

Hours after TMR PlacementROG flux (μg/m2/min)

9

A 2/11/08 A 5/28/08 B 11/20/07 B 2/27/08 B 6/30/08

Figure 7. Total Alcohol (Methanol, Ethanol and Propa nol) fluxes related to time after feed placement from additional TMR flux data sampled as par t of a related project.

Flush Lane Flux Rates Flush lanes are the concrete surfaced areas between the feed bunkers and the bedding stalls in a free stall dairy barn. The cows stand in a flush lane while eating the TMR and much of their manure is deposited in the lanes at that time. Most dairies construct the lanes with a slope so that a large volume of water can be used to flush the lane and remove the manure several times each day. T he flush water drains to a collection and separation facility where the so il particles and coarse fiber in the manure are separated before the water and fine solids are stored in a lagoon. Water from the lagoon recycles for subsequent flushing operations. A few dai ries remove the manure with a vacuum truck (Dairy E) or scrape it in to pits (Dairy F) to elimi nate the need for the large volume of flush water.

The largest components of ROG identified in the silage and feed monitoring are alcohols that are very soluble in water and would, therefore, not be expected to be as volatile from an aqueous medium compared to a soil or concrete surface. The emissions from the lane after flushing are low as is shown by the Post-flush averages in Table 7. The fresh manure also has a signi ficant water content and might also produce lower emissions of alcohols and other soluble ROG species. The flux rates for flush lanes are generally much lower than t hose of feed or feed components. The

24exceptionally high ROG tota l for Dairy A on 2/15/08 appear s to be an anomaly. The total ROG for that samp le exceeds the next highest by a fa ctor of 4 and is more than 10 times the average flux rate. Though the alcohols and DMS are higher than other samples, the high rate is due primarily to CF C-12, a refrigerant gas that was not found in other samples at more than trace conc entrations. It remains to be determined whether this is an error or an example of a sporadic phenomenon. Other samples were taken on that date that may help explain t hese anomalous values in the comprehensive report. In the event that th is one sample is not represent ative, the flush lane averages were recalculated without Dairy A on t hat date and are shown in Table 8.

In general, the pre-flush flux rates are about 10% or less compared to those from TMR and silage. The post-flush flux rates are about 1% of those from fe ed. The rates from the individual dairies were fairly consist ent and the differences between the flush dairies (A, B, C, and D) compared to vacuum (E) and scraping (F) were less than expected. The two dairies that did not use flush wate r were lower than the average of the flush dairies but only slightly so and the differences may not be statistically significant. Additional data from the rela ted projects may result in more definitive evaluation of emissions from flush vs. scraped or vacuumed manure management.

Table 7. Average flush lane flux rates for ROG. Values are averages for each dairy from samples taken prior to flushing unless s pecified as “Post-flush”. The significantly higher values for Dairy A are from one sampli ng event on 2/15/08. See text for further explanation. Individual data averaged for this table can be found in Appendix A, Table A4. Values are in μ g/m 2 /minute and are corrected by subtra ction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Average of all dairies Surface Air Flush Lane (Pre-Flush) 17.1 17.9 353 22 9 108 47% 20 7 0 12 Flush Lane (Post-Flush) 12.9 15.8 21 3 1 6 53% 0 0 0 0

A 16.1 14.3 1,402 95 8 374 27% 67 10 0 71
B 16.6 18.0 246 13 9 66 51% 2 4 0 3 C 17.7 18.8 275 9 1 58 38% 38 4 0 5
D 16.1 18.9 116 12 29 83 72% 2 5 0 0
E 15.3 15.8 181 9 5 65 38% 18 17 0 3
F 20.3 20.6 129 12 6 75 58% 4 5 0 2 Ambient Temperature (degrees C)

25Table 8 . Average flush lane flux rates for ROG. Values are averages for each dairy as in Table 7 with the possibly anomalous data from Dairy A on 2/15/08 deleted. Individual data averaged for this table can be found in Appendix A, Table A4. Values are in

μ g/m 2 /minute and are corrected by subtra ction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Average of all dairies Surface Air Flush Lane (Pre-Flush) 17.1 17.9 241 22 9 108 47% 20 7 0 12 Flush Lane (Post-Flush) 12.9 15.8 21 3 1 6 53% 0 0 0 0

A 16.1 14.3 207 12 9 69 27% 13 7 0 3
B 16.6 18.0 246 13 9 66 51% 2 4 0 3 C 17.7 18.8 275 9 1 58 38% 38 4 0 5
D 16.1 18.9 116 12 29 83 72% 2 5 0 0
E 15.3 15.8 181 9 5 65 38% 18 17 0 3
F 20.3 20.6 129 12 6 75 58% 4 5 0 2 Ambient Temperature (degrees C)

Open Lot, Exercise Pen and Corral Flux Rates Each dairy has some open uncovered areas t hat the cows can access from the free stalls. Some of the dairies (B and D) hav e very large open lots, others (C and F) have much smaller corrals. Except in the winter when access ma y be restricted, most of the manure that is not deposited in the flush lane will fall in the open lot. Animals tend to concentrate in parts of the corral where the manure pack will be relatively deeper than areas they do not frequent. Flux chamber samp ling of fluxes in these open lots included both shallow and deep manure pack areas. The flux rates were expected to be different across the open lot and the average flux rate for the deep pack areas was higher than that of the shallow pack locations.

Table 9 shows the averages for shallow an d deep samples as well as the averages for each dairy. The flux rates for deep pack locations averaged about twice that of the shallow pack areas. It shoul d be noted that most open lots are harrowed or disked for fly and odor control occasionally during dry weather and thes e practices are very likely to affect flux rates from open lots.

Dairy E had a much higher average flux rate for the deep pack areas. This high average was due to the two deep pack samples taken on 6/21/07 in which the alcohols were similar to other samples but the acetaldehyde and di-methyl sulfide levels exceeded the average flux rates of the other dairies by an order of magnitude. The shallow pack sample for that date was also t he highest of all sampled locations. Further analysis of the data from the related projects may be able to explain the high rates for this date.

26The average flux rates for open lots are com parable to those of the flush lanes though the larger area represented by open lots at most of the dair ies makes them, potentially, a more significant source. Further analysi s with the additional dat a from the related projects should provide more detailed eval uation of the differences between open lot conditions and may suggest management practices that might result in reduced emissions.

Table 9. Open lot, exercise pen and corral flux averages. Fluxes are averaged from the individual samples found in Appendix A, Table A5. Shallow manure pack indicates samples taken from an area where the deposited manure was 0 – 5cm deep. Deep manure pack samples were from areas w here the manure was 5- 15cm deep. Values are in μ g/m 2 /minute and are corrected by the subt raction of Field Blank values.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

Average of all dairies Surface Air Open Lot Shallow Manure Pack 25.2 21.0 102 15 17 45 56% 35 1 0 12 Open Lot Deep Manure Pack 24.4 21.1 243 20 28 60 57% 69 1 0 74

Average of each dairy - shallow manure pack
A 25.9 21.3 109 16 20 55 64% 35 0 0 13
B 23.5 21.0 63 15 12 29 61% 16 0 0 12 C 32.0 26.4 75 11 21 48 60% 17 1 0 5
D 23.9 21.3 150 26 11 75 57% 33 2 0 9
E 25.7 20.6 167 8 30 42 46% 95 1 0 24
F 21.2 15.8 36 8 7 20 44% 4 1 0 7

Average of each dairy - deep manure pack
A 21.7 18.2 92 17 25 44 61% 30 0 0 6
B 21.9 21.0 211 21 25 52 61% 5 1 0 37 C 36.1 24.8 127 15 19 51 43% 53 2 0 11
D 23.1 19.5 174 31 22 72 60% 27 2 0 17
E 26.6 23.6 616 11 49 75 48% 254 1 0 280
F 22.6 20.6 96 27 18 59 60% 8 1 0 20 Ambient Temperature (degrees C)

Correlations With Ambient Conditions The first samples collected in 2005-6 were upwind and downwind air samples described in the Year-1 program (Appendix B). This procedure was eliminated for the Year-2 sampling program for reasons de scribed above. There were two specific objectives for the ambient air sampling in Year-1 and t he first was achieved while the second was unsuccessful. The use of ambient samples to characterize the range of specific components of dairy ROG emissions was quit e useful. The unexp ected predominance of alcohols first found in a study at UC Davis was confirmed by these field samples. The initial round of air samples also allowed the UC Irvine lab to calibrate their analytical systems and develop standards for dairy air emissions work. Dr. Blake’s lab had not analyzed samples of this type prior to th is project and some calibration was needed before quantifiable results could be used with confidence. Table A6 shows the average

27of 59 ambient samples analyzed in Year-1. The very high values for alcohols may be inflated by some of the first analyses w here the lab systems had not yet been properly standardized to the appropriate concentrations. The significance of data in Table A6 is the identification and relative magnitude of the various ROG components. The concentration values were often higher for the upwind or background samples than for the dairy downwind samples due to the variable wind speed and direction discussed previously. These data should not be used as examples of specific dairy emissions but are valuable for the identific ation of the components of R OG in the ambient atmosphere of the dairy areas of the Central Valley.



### DISCUSSION

The four dairy operations sampled for this st udy were selected by the project’s advisory group after consideration of data from the initial year of the study. Though lagoons were originally considered to be a major sour ce of ROG, these four, silage, TMR, flush lanes and open lots, proved to be more signifi cant sources and so were emphasized in the Year-2 monitoring program. Fluxes for the four sources, averaged for all six dairies and each date are shown in Table 10.

Of these four sources, silage has the highes t flux rate, closely followed by TMR with flush lanes and open lots at much lower rate s. The high flux from silage should be considered in light of the difference between the compressed material in the pile and the disturbed silage pulled fr om the pile to be used in the next TMR. Silage piles can be hazardous as they are often mo re than 10m high. The highly compressed material in the pile is generally so consol idated that the pile face, w here material is pulled for TMR is usually vertical and may actually over hang the working area below the face. The compaction is never completely uniform and unstable areas of the pile are unavoidable. An unexpected fall of material from hi gh on the face is not uncommon and can be dangerous. Consequently, the silage is usually pulled down in just a few operations each day to minimize the exposure of worker s to the danger of a silage avalanche. A large amount of compressed silage is theref ore often disturbed to be used over a day or more of TMR mixing. While it is apparent from this data that silage should be left undisturbed as much as possible to minimize ROG emissions, that may be contrary to safe working practices. The emissions from disturbed silage ar e high; however the amount of material and the area of the emission is small com pared to other sources. The average flux rate for undisturbed silage material shown in Table 10 is about 22% of the flux rate from disturbed silage. A typical dairy might have a silage pile with an exposed face of 250 m 2 with a loose pile of disturbed s ilage at its base of only about 25

m 2 . The total ROG flux from the silage operation woul d therefore be primarily due to the lower flux from the larger area of undisturbed pile face. A considerable amount of additional silage data will be available when t he related projects are complete, including more flux data, silage analysis and density as well as pile dimensions for each of the six dairies. More detailed correlations will be possible with that additional data when the comprehensive report is completed.

28Table 10. Average flux rates for all dairies, a ll dates and each dairy operation included in the regular sampling program for Year-2 . The 6 major constituents of ROG are reported here with the rema ining components grouped as “o ther”. The UC Irvine analysis included ROG components from a list of 64 gasses identified in the analytical procedure. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.Total ROGEthanolMethanolAlcoholsAlcoholsAcetaldehyded-Lim oneneDMDSDMSOther

Open Lot Shallow Manure Pack 102 15 17 45 56% 35 1 0 12 23 Open Lot Deep Manure Pack 243 20 28 60 57% 69 1 0 74 50 Lagoons 36 5 2 7 20% 4 0 0 0 25 Flush Lane (Pre-Flush) 353 22 9 108 47% 20 7 0 12 283 Flush Lane (Post-Flush) 21 3 1 6 53% 0 0 0 0 16

TMR (0.5 h Post Placement) 15,022 11,668 1,460 13,141 86% 336 584 26 831 117 TMR (6 h Post Placement) 10,582 7,747 1,591 9,350 87% 469 557 9 152 55 TMR (6+h Post: consumed) 2,929 2,289 389 2,683 89% 106 102 3 32 9

Silage Pile Undisturbed Face 4,229 3,095 416 3,524 86% 164 6 1 532 16 Silage Pile Disturbed Face 19,170 12,814 632 13,461 84% 214 49 1 5,413 47

A few flux chamber samples were collected from lagoon surfaces for a related project funded by the California Dairy Campaign. T hese lagoon fluxes do not correspond to the sampling periods reported above but they ar e shown in Table 10 and Figure 8 to illustrate the relative insignificance of l agoon emission rates compared to other dairy sources of ROG. These lagoon emission rates were monitored at Dairies A and D in May and November, 2007 to compare with lagoons at three other dairies, not included in this CARB study. More complete dat a related to lagoon emission composition and rates will be included in the comprehensive report.

290 5,000 10,000 15,000 20,000 25,000 Open Lot Shallow Manure Pack Open Lot Deep Manure Pack Lagoons Flush Lane (Pre-Flush) Flush Lane (Post-Flush) Total Mixed Ration (0.5 h Post Placement) Total Mixed Ration (6 h Post Placement) Total Mixed Ration (6+h Post: consumed)

Silage Pile Vertical Undisturbed Face Silage Pile Disturbed Face

ROG flux ( μ g/m 2 /minute)

Figure 8. ROG fluxes averaged fr om each dairy and sampling date. These data are from the Total ROG column of Table 10.

300 2,000 4,000 6,000 8,000 10,000 12,000 14,000Total Mixed Ration(0.5 h PostPlacement)Total Mixed Ration(6 h PostPlacement)Total Mixed Ration(6+h Post:consumed)Silage Pile VerticalUndisturbed FaceSilage Pile DisturbedFaceflux (μg/m2/minute)

Ethanol Methanol Acetaldehyde d-Limonene DMDS DMS Other Figure 9. Fluxes of the six prominent, s pecific ROG components of emissions, compared to the minor components (other) from feed and silage. This data is from the TMR and Silage lines of Table 10.

The feeding operation has fluxes nearly compar able to those from silage, as would be expected from the fact that silage is t he major component of t he TMR and the mixing process thoroughly disturbs a ll the components. The data for TMR shown in Table 10 and Figures 8 and 9 reflects the complexity of TMR fluxes of ROG that were not completely understood until the Year-2 program was in progress. It was apparent that fluxes from TMR were high when the material was initially placed in the feed bunker. Consecutive samples in a related project using the real-time INNOVA analyzers showed decreasing flux chamber concentrations for al cohols, minute by minute, over the first monitoring period, 30-60 minutes post-placemen t. Project staff noted the distinctive odor from the TMR decreased rapidly from t he time of placement. Two factors were probably responsible for this decrease in flux. The animals consumed feed and the volatility appeared to decrease rapidly as the TMR was spread out and exposed to the air.

This apparent decrease in flux with time was monitored prior to Year-2 by following the initial, post-placement sample with another at 1.5 hours, post-placement. The flux values for these later samples were lower; about 30% of the initial fluxes. The advisory group, after consideration of this data, requested a more thorou gh evaluation of the

31TMR. The group considered TMR to be, po tentially, the largest ROG source, and, perhaps the most complex, variable and m anageable. The Year-2 program included samples at each diary for the beginning (0.5 hours) and end (6 hours) of the feeding period and, if possible a flux from the su rface after the TMR was consumed. The averages for that portion of the Year-2 pr ogram (Table 5) do not appear to match the rapid decrease in flux shown by the earlier 1.5 hour post-placement fluxes. A potential reason for this involves an additional prac tice in the feeding oper ation. The large amount of TMR placed initially in the feed bunker is consumed most rapidly in the first hour or two. The cows return to the bunker later to eat the remain ing feed. It is a common practice to scrape or sweep the rem nants of the TMR into a more accessible pile about 4 – 6 hours after placement. T he 1.5 hour samples in Table 5 were taken prior to that sweeping and the 6 hour samples were usually following such a practice. The sweeping operation disturbed the material and expo sed previously buried TMR to the air. The odor of the feed was noticeab ly stronger after sweeping and the fluxes were higher.

This phenomenon became apparent early in the Year-2 program and had, in fact, been anticipated by the advisory group. The emphasis on TMR fluxes included a more detailed sampling program at Dairies A and B, referred to as the “special sampling” described in Appendix B. While that spec ial sampling was done as part of the related projects, some UC Irvine samples were inclu ded when there were sufficient canisters. Though much of the data for t he special samples is not ye t available, the UC Irvine analysis is shown in graphic form in Figures 6 (ROG) and 7 (total alcohols). The continuous sampling from placement to comp lete consumption of the TMR is shown over an 8 hour span. The fluxes at 8 hours are for the bunker surface after complete consumption. The spike in flux rate at 6 hours seen in the regular sampling is not as apparent in these special samples. Further correlation with additional data may explain the reasons for this.

Flush lane fluxes were originally expect ed to be the major source of ROG from the animal housing areas. In fact, flux rates from flush lanes are less than 5% of the average TMR flux when the amount of manure is greatest, prior to flushing. When the lanes have been flushed, scraped or vacuumed, the flux rate is less than 0.3% of the average TMR rate. The composition of the ROG fl ux is also different for the flush lanes. While the alcohols are still the dominant components, they are about half of the ROG from the lanes compared to t he 80% - 90%+ alcohols in flux es from silage and TMR. Propanol was a much greater component of the fresh manur e in the pre-flush lane compared to the other s ources. The area of flush lanes in the dairy barn is greater than that of the feed bunker by a factor of 5 – 10. The relative fluxes from these two sources are therefore, less different t han their flux rates would indi cate but the flush lanes are still significantly smalle r sources than the TMR.

Fluxes of ROG from the open lots, shown in Table 9, ar e lowest of the four sources sampled in this project. The open lots are al so the most variable in size, composition, pattern of use and management practices. The variability in average flux among the dairies was actually less than expected and was comparable to that of the flush lanes.

32The composition of the ROG emission was al so similar to the flush lanes with some notable differences. The alcohols made up about half of the ROG emission as with the lanes though ethanol and methanol were respons ible for nearly all the alcohols in relatively equal proportions in the manure pack of the open lots. T hough the flux rates are comparably low for the open lo ts, the larger area increases their significance as an ROG source. Some dairies have very large lots (10,000 m 2 or more) and some are quite small (2000 m 2 or less). The differences in size, coupled with different management practices and loading will make es timates of emissions from open lots more difficult than the other sources. A dditional data and manageme nt information will be included in the comprehensive report.



### SUMMARY and CONCLUSIONS

There were three basic questions that led to the original proposal to CARB for this project and the subsequent revisions by the advisory group. 1. What are the components of ROG emissions from dairy operations in California? 2. What are the most significant source s of ROG related to dairy operations? 3. Are there procedural and seasonal e ffects on ROG from California dairies?

The first question was the first priority si nce the composition of dairy emissions was unknown and needed to be characterized in order to select the appropriate methods of sampling and analysis for the Year-2 progr am. The initial do wnwind-upwind sampling and analysis at UC Irvine was successful in that characterization. The data from those first year samples is shown in Appendix A, Table A6. Once the major components and their relative concentrations were determi ned, the analytical procedures at UC Irvine could be optimized for dairy air samples an d analytical standards could be prepared. While there are certainly other VOC’s that might have been present in these samples that could react as ozone precursors, it was assumed that all significant components of ROG were identified and quantifi ed by Dr. Blake at UC Irvine. The identification of alcohols as the major component of ROG em issions from each dairy operation was the first significant conclusion of this project. Th at led to several related projects to monitor alcohols with additional met hods of sampling and analysis.

Once the composition of dairy ROG emissions had been determined, the second question of identifying the rela tive magnitude of emissions from the various dairy operations could be addressed. The initial downwind-upwind sa mples that were of such value in characterizing the ROG com ponents could not discriminate between the separate sources within the animal housing areas and so the advisory group directed the sampling program’s change to the use of flux chambers. Fluxes measured by this chamber method are specific to the surface and the area on which they are placed for a particular sample. Multiple measurements over both time and area are required to determine the magnitude and variability of th e flux from a surf ace and the limited number of UC Irvine analyses that was avai lable in this project budget was not adequate to accomplish this for every sa mpling location and period. The other sampling/analysis methods added for the re lated projects will be important for the further characterization of each location. It is possible, as an academic exercise, to

33estimate the relative flux magnitudes with the UC Irvine data reported here and that will also serve as an example of the conver sion procedures that may be possible with additional data in the comprehensive report.

The flux rate averages in Table 10 can be us ed to illustrate the calculation of emissions to the degree that the relati ve magnitude of each source can be compared. In the discussion of the silage source above, an exam ple was given to illustrate the proportion of ROG emissions from disturbed and undisturbed silage. That example can be carried further and used for the other sources as well at a fictitious 2000 cow dairy that might be imagined from a composite of the six facilities sampled in this project. This fictitious dairy has four barns, each 400m long, with a feed bunker, two flush lanes and a large open lot. The areas of those sources, comb ined with the ROG flux rates from Table 10 can be used to illustrate the relative magnitudes of fluxes from a dairy as well as serve as an example of how fluxes can be combined with specific dairy dimensions to calculate emissions from a specific facility.

Disturbed Silage Average flux (Table 10) = 19,170 μ g/m 2 /minute Estimated area at the fictitious dairy = 25 m 2 Estimated emission = 19,170 μ g/m 2 /minute X 25 m 2 X 1440 min/day = 0.7 kg/day

Undisturbed Silage Average flux (Table 10) = 4,229 μ g/m 2 /minute Estimated area at the fictitious dairy = 250 m 2 Estimated emission = 4,229 μ g/m 2 /minute X 250 m 2 X 1440 min/day = 1.5 kg/day

TMR (average of all sample periods) Average flux (Table 10) = 8,260 μ g/m 2 /minute Estimated area at the fictitious dairy = 1600 m 2 (1m wide x 400m long x 4 bunkers) Estimated emission = 8,260 μ g/m 2 /minute X 1600 m 2 X 1440 min/day = 19.0 kg/day

Flush lanes (average of pre-flush and post-flush) Average flux (Table 10) = 187 μ g/m 2 /minute Estimated area at the fictitious dairy = 9600 m 2 (3m wide x 400m long x 8 lanes) Estimated emission = 187 μ g/m 2 /minute X 9600 m 2 X 1440 min/day = 2.6 kg/day

Open Lots (average of deep and shallow manure pack) Average flux (Table 10) = 172 μ g/m 2 /minute Estimated area at the fictitious dairy = 32,000 m 2 (20m wide x 400m long x 4 lots) Estimated emission = 172 μ g/m 2 /minute X 32,000 m 2 X 1440 min/day = 7.9 kg/day

ROG emissions from the fictitious dairy and their relative percentages of the total: Disturbed Silage...... 0.7 kg/day (2%) Undisturbed Silage... 1.5 kg/day (5%) TMR.................... 19.0 kg/day (60%) Flush lanes............. 2.6 kg/day (8%) Open Lots.............. 7.9 kg/day (25%) Total ....................31.8 kg/day (100%)

34This estimation does show the fact that the TMR is the largest ROG source at the dairy (60%) followed by the open lots (25%), t he flush lanes (8%) and the silage (5% for undisturbed and 2% for disturbed material). While these percentages will change for specific facilities, TMR is likely to remain the dominant source. T here is a considerable amount of TMR flux data from the related projects that s hould produce a more accurate average as well as a better evaluation of t he variability and relationship to feed components and other feeding practices. It is clear that reductions in TMR fluxes have the most potential to mitigat e dairy emissions of ROG.

TMR 60%

Silage (undisturbed) 5% Silage (disturbed) 2% Flush Lanes 8% Open Lots 25%

Figure 10. An example of the rela tive ROG source magnitudes at a fictitious dairy. These proportional values are calculated from the averaged flux rates for all six dairies for all sampling periods in Year-2, multiplie d by the averaged areas of those sources for the six dairies. These are shown to illustrate the relative magnitude of the ROG sources Specific source rates and propor tions will be different for different dairies and seasons.

This example calculation is not intended for us e as an emission factor for dairies. The dimensions do not represent any specific facility and the fluxes are averages of a number of sampling events that have considerable variation. Another factor that must be considered is the nature of the flux chamber method. Flux chamber data can be

35used to calculate ROG emissions from a surfac e into the artificial, zero-air atmosphere of the chamber, immediately above the surface being sampled. Any atmospheric reactions that might occur wit h a flux into an ambient atmosphere or adhesive effects between ROG and surfaces at the dairy are not reflected in t hese results. Atmospheric and surface effects on the ROG components w ould probably reduce the concentrations so these reported flux values are most likely an overestimation of the emissions from these operations, especially those that take place in the barn areas. Downwind-upwind sampling or other similar monitoring me thods would be required to determine the differences between the flux from these su rfaces as measured by the flux chamber method and the actual emissions after the po st-surface emission reactions have been included. That level of monitoring was beyond the scope of this project but is being conducted by other research groups in California and elsewhere.

Correlation of ROG flux rates with ambient conditions was one of the primary objectives of the original proposal. The winter, summe r and fall sampling periods were selected to evaluate an expected seasonal effect on flux rates for the different dairy locations and operations. It was assumed t hat higher temperature surfac es would volatilize higher rates of emissions during warm weather. Th e only example where this is apparent with the data reported here is related to the open lots. Both the shallow and deep manure pack locations showed a strong, positive correla tion with the temperatur e of the surface. Table A5 in Appendix A shows open lot surface temperatures ranging from 39.5 C down to 9.3 C. The higher flux rates were consistently found at the higher surface temperatures in both shallow and deep pack areas. Additional emissions and manure samples were collected for these areas by th e related projects and will be statistically evaluated in the comprehensive report. Further data analysis may show other correlations with surface or ai r temperature but the open lots are the only areas where the correlation is obvious from the CARB data.



### Recommendations

Recommendations for further research are, for the most part, rela ted to the additional projects that were begun during the course of this study wit h the additional support from CSU ARI and the cooperating researchers described above. Completion of these related projects in the next year should si gnificantly expand the data set and provide much more detailed conclusions with regard to fluxes of ROG and other gasses. The more intensive study of emissions from dairy operations recommended in the Summary and Conclusions section are necessary to de termine the fate of R OG between emission from the source surface as m easured by the flux in this study and the point at which the ROG is emitted from the dairy facility. Some studies of that nature are in progress and more should be encouraged to fully evaluate dairy ROG emissions.

The speciation of ROG emissions from dairies t hat was the first object ive in this project is only the first step in characterizing t hese sources with regar d to their potential contribution to ozone formation. These R OG species are different, not only by composition but also in their ability to participate in the ozone formation reaction. Some

36components may be present in significant amounts but have little effect on ozone formation because of a low reactivity. Other ROG’s may be present in smaller amounts but be more significant precursors of oz one due to a higher reactivity. A complete evaluation of dairy emissions as they affe ct ozone formation will need to include the reactivity of these specific ROG’s as we ll as their relative emission rates.



### References

This study, as a data collection project, di d not include a literature review in the proposal. An extensive review of current research was completed by members of the project advisory group as part of the contemporary DPAG activity. Though that review of literature was import ant to the planning and execution of this study, it was not done as part of this CARB funded activity and is not reported in this document.

The Dairy Permitting Advisory Group of the San Joaquin Valley Air Pollution Control District completed an extensive review of re search related to dairy emissions in 2005, as this project was beginning. The public agency and industr y members of the CARB/CDFA Dairy Sub-committee that became the advisory group for this project were also DPAG members. The research me mbers of this project’s advisory group participated in the DPAG process as well. The review of research and DPAG discussions were integral to t he development of this project, especially the revisions to focus on ROG emissions, recommended by the advisory group as it progressed. A review of research and literature beyond that done for the DPAG report would have been superfluous. The DPAG report, with an extensive list of references may be found at:

<http://www.valleyair.org/busind/pt o/dpag/DPA_%20EF_Report_Final.pdf>



### List of Inventions and publications produced

No inventions or patentable processes were dev eloped in the course of this project. No

publications based on this data have yet been s ubmitted by any of the investigators or cooperators. Several publicat ions are expected to be submitted by collaborators and cooperators when the related projects are co mpleted and the full data set is available.

37

### APPENDIX A

The following tables list the individual samples collected by CSU Fresno and analyzed at UC Irvine that were averaged and summarized in the Results section. Only samples with corresponding field blanks are reported here. A sma ll number of other samples were analyzed at UC Irvine for the special sa mpling and related projects but do not have UC Irvine field blanks and so cannot be evaluat ed until other QC data is available.

38Table A1 . Silage samples from material dislodged from the pile for use in the next TMR mix. Values are fluxes in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values. The 6 major components of ROG are reported here. The UC Irvine analysis included ROG components from a list of 64 gasses identified in the analytical procedure.

Dairy Date Surface Description Surface Temp. Air Temp.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

A 06/11/07 Silage Pile Disturbed Face 35.3 31.5 8,209 6,564 1,438 8,002 97% 76 49 1 0 A 09/25/07 Silage Pile Disturbed Face 25.3 26.2 17,068 13,471 1,694 15,212 89% 739 63 1 1,042 A 02/08/08 Silage Pile Disturbed Face 22.9 12.1 34,875 23,458 1,286 24,779 71% 509 199 1 9,246 A 06/02/08 Silage Pile Disturbed Face 19.3 20.1 15,919 8,510 1,114 9,634 61% 596 837 1 4,818 B 10/02/07 Silage Pile Disturbed Face 18.6 14 2,823 2,369 348 2,743 97% 64 9 1 10 B 02/19/08 Silage Pile Disturbed Face 28.8 12.6 3,546 3,041 442 3,482 98% 11 1 1 59 B 07/02/08 Silage Pile Disturbed Face 18.9 19.6 2,512 2,265 186 2,451 98% 23 0 1 32 C 06/25/07 Silage Pile Disturbed Face 30.8 27.3 56,107 55,797 46 55,843 100% 184 0 1 0 C 10/30/07 Silage Pile Disturbed Face 31.7 16.8 9,859 8,724 671 9,414 95% 440 5 0 1 C 04/09/08 Silage Pile Disturbed Face 15.2 12.1 6,105 4,145 569 4,757 78% 164 1 1 1,169 C 06/17/08 Silage Pile Disturbed Face 20.7 18.8 72,698 70,645 935 71,591 98% 425 31 1 633 D 10/23/07 Silage Pile Disturbed Face 23.7 16 83 82 5 86 104% 4 0 0 0 D 03/14/08 Silage Pile Disturbed Face 14.6 10.1 8,670 7,776 466 8,251 95% 44 20 1 351 D 06/26/08 Silage Pile Disturbed Face 32.5 24.4 60,816 13,189 1,456 14,707 24% 124 0 7 45,922 D 03/22/07 Silage Pile Disturbed Face 27.8 20 5,103 4,722 304 5,026 98% 0 0 1 55 D 07/24/07 Silage Pile Disturbed Face 39 32 18,425 18,283 62 18,346 100% 32 1 1 1 E 06/20/07 Silage Pile Face disturbed 38.8 24.9 28,187 27,829 48 27,877 99% 50 0 1 0 E 10/16/07 Silage Pile Disturbed Face 21.5 14.1 814 228 451 681 84% 134 0 0 1 E 03/10/08 Silage Pile Disturbed Face 15.4 9.2 16,023 5,857 784 6,656 42% 31 1 1 9,316 E 06/09/08 Silage Pile Disturbed Face 32.7 25.5 10,132 7,846 936 8,801 87% 89 1 1 1,227 F 04/17/07 Silage Pile Disturbed Face 18.8 18.4 1,477 1,274 197 1,471 100% 0 0 1 3 F 07/17/07 Silage Pile Disturbed Face 19.4 22 6,104 6,054 40 6,094 100% 4 0 0 0 F 11/06/07 Silage Pile Disturbed Face 18.2 14.8 4,845 3,321 260 3,581 74% 1,259 0 1 6 F 03/28/08 Silage Pile Disturbed Face 11.2 11.7 12,859 9,336 677 10,026 78% 111 1 1 2,719 F 07/09/08 Silage Pile Disturbed Face 29.5 30.8 75,977 15,572 1,393 17,015 22% 232 0 1 58,710

Dairy Averages A 25.7 22.5 19,018 13,001 1,383 14,407 80% 480 287 1 3,776 B 22.1 15.4 2,961 2,558 325 2,892 98% 32 3 1 34 C 24.6 18.8 36,192 34,828 555 35,401 93% 303 9 1 451 D 27.5 20.5 18,620 8,810 459 9,283 84% 41 4 2 9,266 E 27.1 18.4 13,789 10,440 555 11,004 78% 76 1 1 2,636 F 19.4 19.5 20,252 7,111 513 7,637 75% 321 0 1 12,287

39Table A2 . Silage samples from undisturbed ma terial. Values are fluxes in

μ g/m 2 /minute and are corrected by t he subtraction of Field Blank values. The 6 major components of ROG are reported here. The UC Irvine analysis included ROG components from a list of 64 gasses ident ified in the analytical procedure.

Dairy Date Surface Description Surface Temp. Air Temp.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

A 09/25/07 Silage Pile Vertical Undisturbed Face 27.3 25 5,426 4,256 858 5,133 95% 265 3 1 22
A 02/08/08 Silage Pile Vertical Undisturbed Face 32.9 15 6,811 4,539 663 5,234 77% 304 13 0 1,248
A 06/02/08 Silage Pile Vertical Undisturbed Face 20.7 24.2 2,305 1,931 198 2,133 93% 8 15 0 143
B 02/19/08 Silage Pile Vertical Undisturbed Face 23.9 13.4 5,442 4,055 337 4,391 81% 9 2 1 1,046
B 07/02/08 Silage Pile Vertical Undisturbed Face 20.4 21.5 5,713 5,026 228 5,255 92% 23 0 1 431
C 10/30/07 Silage Pile Vertical Undisturbed Face 26.8 17.2 2,090 1,591 234 1,832 88% 247 8 0 3
C 04/09/08 Silage Pile Vertical Undisturbed Face 24.6 13.8 9,729 6,271 968 7,249 75% 88 3 1 2,361
C 06/17/08 Silage Pile Vertical Undisturbed Face 20.1 20.6 4,286 2,954 285 3,238 76% 121 5 1 921
D 10/23/07 Silage Pile Vertical Undisturbed Face 40.2 21.4 8,713 6,029 1,194 7,345 84% 1,322 35 0 4
D 03/14/08 Silage Pile Vertical Undisturbed Face 12.2 12 3,536 2,849 201 3,050 86% 9 2 1 474
E 10/16/07 Silage Pile Vertical Undisturbed Face 15.8 14 1,668 1,404 219 1,625 97% 33 0 0 9
E 03/10/08 Silage Pile Vertical Undisturbed Face 19.9 11.5 2,442 1,966 282 2,251 92% 15 3 1 168
E 06/09/08 Silage Pile Vertical Undisturbed Face 28.9 25 3,798 2,022 380 2,406 63% 24 2 0 1,362
F 11/06/07 Silage Pile Vertical Undisturbed Face 17.4 17.3 1,251 953 164 1,118 89% 132 0 1 2
F 03/28/08 Silage Pile Vertical Undisturbed Face 13 13.1 1,971 1,699 159 1,858 94% 2 1 1 108
F 07/09/08 Silage Pile Vertical Undisturbed Face 29.4 31.7 2,492 1,973 285 2,258 91% 25 0 1 207

Dairy Averages
A 27.0 21.4 4,848 3,575 573 4,167 88% 192 11 1 471
B 22.2 17.5 5,577 4,540 282 4,823 86% 16 1 1 738
C 23.8 17.2 5,368 3,605 496 4,107 79% 152 5 1 1,095
D 26.2 16.7 6,124 4,439 697 5,198 85% 665 18 0 239
E 21.5 16.8 2,636 1,798 294 2,094 84% 24 2 0 513
F 19.9 20.7 1,905 1,542 203 1,745 91% 53 0 1 106

40Table A3 . Individual samples of feed (TMR) fluxes. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.

Dairy a t

e Surface Description Surface Temp. Air Temp.Total ROGEthanolMetanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

A Total Mixed Ration (0.5 h Post Placement) 10,561 4,634 3,028 7,662 73% 29 2,747 16 0 A Total Mixed Ration (1.5 h Post Placement) 6,994 2,736 1,810 4,547 65% 33 2,288 18 0 A Total Mixed Ration (0.5 h Post Placement) 25.9 18.8 12,148 6,699 2,527 9,257 76% 1,178 1,650 1 4 A Total Mixed Ration (6 h Post Placement) 23.2 26.4 13,269 6,927 3,076 10,030 76% 1,313 1,825 0 4 A Total Mixed Ration (6+h Post: consumed) 22.5 27 2,488 1,338 796 2,140 86% 77 266 0 1 A Total Mixed Ration (0.5 h Post Placement) 19.2 10 10,250 4,293 2,485 6,812 66% 146 2,478 41 543 A Total Mixed Ration (6 h Post Placement) 13.6 15 6,620 2,765 1,919 4,705 71% 69 1,649 12 80 A Total Mixed Ration (6+h Post: consumed) 7.7 5.6 1,200 799 255 1,056 88% 83 45 1 11 A Total Mixed Ration (0.5 h Post Placement) 24.2 19.6 32,477 22,553 5,073 27,637 85% 268 3,722 32 591 A Total Mixed Ration (6 h Post Placement) 22 23.7 16,390 11,648 2,302 13,955 85% 251 2,053 7 55 A Total Mixed Ration (6+h Post: consumed) 18.4 17.5 6,069 3,951 1,281 5,233 86% 190 615 3 18 B Total Mixed Ration (1.5 h Post Placement) 3,114 2,384 646 3,029 97% 0 0 1 63

B Wet Distillers Grain 13.9 12 830 804 17 821 99% 0 0 0 7 B Total Mixed Ration (0.5 h Post Placement) 22 23 8,309 7,875 225 8,100 97% 46 1 101 0 B Total Mixed Ration (1.5 h Post Placement) 23.5 24.4 2,692 2,530 76 2,607 97% 17 0 37 0 B Total Mixed Ration (0.5 h Post Placement) 24.1 20.1 7,532 5,319 1,088 6,440 86% 1,017 0 0 34 B Total Mixed Ration (6 h Post Placement) 26.8 26.3 7,054 3,543 1,347 4,906 70% 2,091 0 1 22 B Total Mixed Ration (6+h Post: consumed) 21 24.2 681 471 142 613 90% 52 14 0 0 B Total Mixed Ration (0.5 h Post Placement) 24.2 13.1 12,770 7,248 2,898 10,171 80% 56 0 44 2,329 B Total Mixed Ration (6 h Post Placement) 10.8 9.8 1,380 856 480 1,338 97% 23 0 1 14 B Total Mixed Ration (6+h Post: consumed) 9.7 8.8 207 137 63 201 97% 4 0 0 0 B Total Mixed Ration (0.5 h Post Placement) 26.5 26.6 20,125 8,515 3,619 12,134 60% 317 3 152 7,336 B Total Mixed Ration (6 h Post Placement) 24.5 29.2 34,254 27,030 6,025 33,067 97% 372 2 57 711 B Total Mixed Ration (6+h Post: consumed) 24.2 29.8 507 399 77 477 94% 0 0 2 27 C Total Mixed Ration (0.5 h Post Placement) 26.2 11.8 14,327 12,956 691 13,656 95% 503 108 1 2 C Total Mixed Ration (6 h Post Placement) 20.1 19 8,512 6,970 862 7,838 92% 630 0 0 1 C Total Mixed Ration (6+h Post: consumed) 17.6 18.4 2,060 1,575 226 1,800 87% 253 0 0 1 C Total Mixed Ration (0.5 h Post Placement) 13.5 8.9 30,432 27,745 1,042 28,798 95% 630 55 29 790 C Total Mixed Ration (6 h Post Placement) 16.3 16.7 5,040 4,210 502 4,714 94% 288 8 3 15 C Total Mixed Ration (6+h Post: consumed) 14.6 16 3,704 3,408 221 3,631 98% 58 7 2 4 C Total Mixed Ration (0.5 h Post Placement) 19.5 16.3 46,515 45,350 666 46,024 99% 199 5 3 259 C Total Mixed Ration (6 h Post Placement) 20.6 23.4 26,376 24,542 967 25,517 97% 238 26 16 562 C Total Mixed Ration (6+h Post: consumed) 21.4 22.5 2,974 2,629 240 2,871 97% 24 28 2 48 D Total Mixed Ration (0.5 h Post Placement) 20.7 28.1 8,598 6,390 1,100 7,551 88% 965 53 0 2 D Total Mixed Ration (6 h Post Placement) 17.9 24.5 16,483 9,964 2,313 12,324 75% 2,183 1,883 0 2 D Total Mixed Ration (6+h Post: consumed) 20.1 25.5 2,893 1,568 517 2,091 72% 386 407 0 1 D Total Mixed Ration (0.5 h Post Placement) 14.9 10.8 14,446 7,495 1,812 9,318 64% 217 3,883 10 423 D Total Mixed Ration (6 h Post Placement) 14.6 14.6 9,022 4,433 1,668 6,107 68% 124 2,564 3 41 D Total Mixed Ration (6+h Post: consumed) 15.1 15.3 1,821 1,061 301 1,363 75% 22 410 1 16 D Total Mixed Ration (0.5 h Post Placement) 28.2 20.4 35,275 31,263 2,340 33,629 95% 140 0 33 1,424 D Total Mixed Ration (6 h Post Placement) 26.7 24.8 20,460 17,922 1,795 19,732 96% 146 0 32 506 D Total Mixed Ration (6+h Post: consumed) 25.3 25.2 22,859 20,289 1,972 22,276 97% 237 32 29 270 D Total Mixed Ration (0.5 h Post Placement) 30.5 10.6 6,380 5,765 471 6,236 98% 0 21 1 40 D Total Mixed Ration (1.5 h Post Placement) 21.4 14.2 3,720 3,333 322 3,655 98% 0 0 0 39 D Total Mixed Ration (1.5 h Post Placement) 21.4 14.2 3,702 3,313 321 3,634 98% 0 0 1 41 D Total Mixed Ration (1.5 h Post Placement) 21.4 14.2 4,415 3,840 520 4,360 99% 0 21 1 4 D Total Mixed Ration (0.5 h Post Placement) 33.3 24.1 3,001 2,738 0 2,738 91% 24 12 1 0 D Total Mixed Ration (1.5 h Post Placement) 28.4 30.9 3,742 3,589 90 3,679 98% 9 4 1 0 E Total Mixed Ration (0.5 h Post Placement) 23.4 16.9 10,716 10,450 28 10,478 98% 38 0 89 0 E Total Mixed Ration (1.5 h Post Placement) 21.6 21 7,282 7,105 50 7,155 98% 26 0 42 0 E Total Mixed Ration (0.5 h Post Placement) 24.1 20.2 16,237 14,264 710 14,987 92% 1,208 0 1 26 E Total Mixed Ration (6 h Post Placement) 17.6 18.5 2,672 2,507 112 2,622 98% 46 0 0 1 E Total Mixed Ration (6+h Post: consumed) 16.8 17.2 1,730 1,286 40 1,326 77% 402 0 0 0 E Total Mixed Ration (6+h Post: consumed) 16.8 17.2 1,416 1,047 122 1,170 83% 244 0 0 2 E Total Mixed Ration (0.5 h Post Placement) 19.5 21 3,287 2,358 617 2,986 91% 52 0 8 111 E Total Mixed Ration (6 h Post Placement) 15.4 15.3 1,683 1,025 494 1,520 90% 30 3 3 116 E Total Mixed Ration (6+h Post: consumed) 15.2 15.3 1,476 967 466 1,436 97% 11 5 2 21 E Total Mixed Ration (0.5 h Post Placement) 20.2 21.3 12,275 6,007 1,373 7,397 60% 50 13 17 4,784 E Total Mixed Ration (6 h Post Placement) 22.2 28.6 7,179 4,829 1,753 6,599 92% 40 7 18 502 E Total Mixed Ration (6+h Post: consumed) 23.5 27.9 851 500 207 708 83% 5 7 8 122 F Total Mixed Ration (0.5 h Post Placement) 20.6 13.9 1,901 1,493 308 1,800 95% 0 0 1 84 F Total Mixed Ration (1.5 h Post Placement) 19.1 16.9 1,533 1,166 347 1,513 99% 0 0 1 12

F Wet Distillers Grain 42.4 22.5 1,191 1,155 22 1,177 99% 0 0 6 2 F Total Mixed Ration (0.5 h Post Placement) 19.8 18.6 6,137 5,956 141 6,096 99% 19 1 3 0 F Total Mixed Ration (1.5 h Post Placement) 21 20.8 1,385 1,145 53 1,198 86% 5 0 174 0 F Total Mixed Ration (0.5 h Post Placement) 27.1 11.9 5,290 3,817 747 4,577 87% 698 0 2 6 F Total Mixed Ration (6 h Post Placement) 17.5 20.4 2,474 1,569 488 2,064 83% 407 0 1 1 F Total Mixed Ration (6+h Post: consumed) 18.7 21.1 309 236 61 298 96% 11 0 0 0

41Table A4 . Individual flush lane fluxes. The hi gh value for Dairy A on 1/15/08 may be a sampling or analytical error (see text). T he averages for each dairy are calculated both with and without that date. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.

Dairy Date Surface Description Surface Temp. Air Temp.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

A 6/14/2007 Flush Lane (Pre-Flush) 22.9 22.9 45 5 6 16 35% 24 0 0 1 A 2/15/2008 Flush Lane (Pre-Flush)? 8.2 4.5 3,722 238 14 1,025 28% 171 28 0 203 A 6/3/2008 Flush Lane (Pre-Flush)? 17.1 15.6 438 41 5 81 19% 7 2 0 8 B 4/10/2007 Flush Lane (Pre-Flush) 14.9 13.9 40 6 0 14 35% 1 0 0 0 B 7/12/2007 Flush Lane (Pre-Flush) 19.9 19.8 54 10 28 52 97% 0 0 0 0 B 10/4/2007 Flush Lane (Pre-Flush)? 14.9 19.3 26 8 3 11 43% 0 12 0 0 B 3/5/2008 Flush Lane (Pre-Flush)? 11.7 9.2 216 16 3 140 65% 6 4 0 5 B 7/3/2008 Flush Lane (Pre-Flush)? 21.6 27.6 893 24 9 110 12% 5 3 0 8 C 7/3/2007 Flush Lane (Pre-Flush) 23 20.9 164 0 0 12 7% 136 0 0 7 C 11/1/2007 Flush Lane (Pre-Flush)? 15 14.7 97 14 3 78 81% 4 13 0 0 C 4/4/2008 Flush Lane (Pre-Flush) 14 19 102 9 0 55 54% 2 1 0 C 6/16/2008 Flush Lane (Pre-Flush)? 18.7 20.5 735 16 0 86 12% 11 2 0 1 D 10/24/2007 Flush Lane (Pre-Flush)? 17.8 25 77 7 17 59 76% 4 13 0 0 D 3/11/2008 Flush Lane (Pre-Flush)? 13.4 14.2 234 23 66 167 71% 3 2 0 0 D 3/20/2007 Flush Lane (Pre-Flush) 17 17.6 36 6 5 25 68% 0 0 0 0 E 6/21/2007 Flush Lane (Post-Flush) 103 0 2 28 27% 69 1 0 4 E 10/18/2007 Flush Lane (Pre-Flush) 14.4 15.3 175 10 1 110 63% 0 64 0 0 E 3/7/2008 Flush Lane (Pre-Flush)? 11.8 9.9 168 12 11 75 45% 1 3 0 E 6/10/2008 Flush Lane (Pre-Flush)? 19.6 22.1 279 14 5 46 16% 3 2 0 7 F 7/19/2007 Flush Lane (Pre-Flush) 21.2 20.2 88 1 2 78 88% 2 0 0 0 F 11/8/2007 Flush Lane (Pre-Flush) 17.3 20 162 20 4 130 80% 9 17 0 0 F 3/24/2008 Flush Lane (Pre-Flush)? 16.5 15.8 175 14 4 66 38% 4 2 0 1 F 7/10/2008 Flush Lane (Pre-Flush)? 26.3 26.2 93 12 13 25 27% 1 0 0 6 D 10/24/2007 Flush Lane (Post-Flush) 14.4 21.1 8 3 3 6 82% 0 1 0 D 3/22/2007 Flush Lane (Post-Flush) 13 13.8 2 1 0 1 56% 0 0 0 F 4/24/2007 Flush Lane (Post-Scrape) 11.3 12.4 53 5 0 10 19% 0 0 0 1

Average of each dairy Flush Lane (Pre-Flush) 17.1 17.9 353 22 9 108 47% 20 7 0 12 Flush Lane (Post-Flush) 12.9 15.8 21 3 1 6 53% 0 0 0 0

A 16.1 14.3 1,402 95 8 374 27% 67 10 0 71 B 16.6 18.0 246 13 9 66 51% 2 4 0 3 C 17.7 18.8 275 9 1 58 38% 38 4 0 5 D 16.1 18.9 116 12 29 83 72% 2 5 0 E 15.3 15.8 181 9 5 65 38% 18 17 0 3 F 20.3 20.6 129 12 6 75 58% 4 5 0 2

Average of each dairy with Dairy A 2/15/08 deleted Flush Lane (Pre-Flush) 17.1 17.9 241 22 9 108 47% 20 7 0 12 Flush Lane (Post-Flush) 12.9 15.8 21 3 1 6 53% 0 0 0 0

A 16.1 14.3 207 12 9 69 27% 13 7 0 3 B 16.6 18.0 246 13 9 66 51% 2 4 0 3 C 17.7 18.8 275 9 1 58 38% 38 4 0 5 D 16.1 18.9 116 12 29 83 72% 2 5 0 E 15.3 15.8 181 9 5 65 38% 18 17 0 3 F 20.3 20.6 129 12 6 75 58% 4 5 0 2 1
3

1

0
0

0

0

42Table A5 . Open lot, exercise pen and co rral fluxes. Values are in μ g/m 2 /minute and are corrected by the subtraction of Field Blank values.

Dairy Date Surface Description Surface Temp. Air Temp.Total ROGEthanolMethanolTotal AlcoholsTotal AlcoholsAcetaldehyded-LimoneneDMDSDMS

A 06/14/07 Open Lot/Corral (Shallow Manure Pack) 36.5 30.6 243 24 38 65 27% 134 0 0 3
A 09/27/07 Open Lot Shallow Manure Pack 17.2 17.2 38 16 17 34 89% 0 0 0 0
A 02/15/08 Open Lot Shallow Manure Pack 19.0 14.5 36 5 15 21 59% 1 0 0
A 06/03/08 Open Lot Shallow Manure Pack 30.9 22.8 119 17 9 99 84% 3 2 0 8 B 04/10/07 Open Lot/Corral (Shallow Manure Pack) 20.3 15.3 6 4 0 5 78% 0 0 0
B 07/12/07 Open Lot/Corral (Shallow Manure Pack) 31.5 25.5 131 11 14 27 20% 70 0 0 3
B 10/04/07 Open Lot Deep Manure Pack 13.4 13.4 41 25 10 35 84% 5 1 0 0
B 03/05/08 Open Lot Shallow Manure Pack 12.7 10.6 30 4 10 20 66% 1 0 0
B 07/03/08 Open Lot Shallow Manure Pack 39.5 40.2 105 33 26 60 57% 5 0 0 2
C 07/03/07 Open Lot/Corral (Shallow Manure Pack) 38.2 31.2 58 0 5 14 25% 40 0 0 4
C 04/04/08 Open Lot Shallow Manure Pack 23.9 24.4 60 16 31 47 78% 4 1 0 4
C 06/16/08 Open Lot Shallow Manure Pack 33.9 23.5 107 18 28 81 76% 8 2 0
D 10/24/07 Open Lot Deep Manure Pack 16.2 15.1 72 34 30 65 90% 3 3 0 0
D 03/11/08 Open Lot Shallow Manure Pack 16.1 15.2 25 6 14 20 83% 1 0 0
D 06/25/08 Open Lot Shallow Manure Pack 31.0 24.8 378 64 0 212 56% 13 4 0 33 D 07/26/07 Open Lot/Corral (Shallow Manure Pack) 32.4 30.0 125 1 0 1 1% 115 0 0 0 E 06/21/07 Open Lot/Corral (Shallow Manure Pack) 25.4 20.8 501 1 56 57 11% 363 0 0 80
E 10/18/07 Open Lot Shallow Manure Pack 18.3 14.0 57 10 45 55 96% 1 0 0 0
E 03/07/08 Open Lot Shallow Manure Pack 22.7 20.3 14 3 0 3 20% 1 0 0
E 06/10/08 Open Lot Shallow Manure Pack 36.2 27.2 95 19 19 53 55% 15 4 0 13
F 04/24/07 Open Lot/Corral (Shallow Manure Pack) 24.0 18.0 2 0 0 0 0% 0 0 0 0
F 11/08/07 Open Lot Deep Manure Pack 20.3 14.4 16 6 7 13 81% 0 2 0 0
F 03/24/08 Open Lot Shallow Manure Pack 19.3 15.0 91 18 15 48 52% 11 1 0 21

A 06/14/07 Open Lot/Corral (Deep Manure Pack) 28.9 22.7 180 22 28 52 29% 111 0 0 1
A 09/27/07 Open Lot Deep Manure Pack 16.5 14.4 20 4 14 18 91% 0 0 0
A 02/15/08 Open Lot Deep Manure Pack 17.5 14.2 73 11 31 46 62% 2 0 0 5
A 06/03/08 Open Lot Deep Manure Pack 24.0 21.4 93 31 27 58 63% 6 1 0 6
B 04/10/07 Open Lot/Corral (Deep Manure Pack) 24.5 22.4 22 14 0 14 62% 0 0 0 5
B 07/12/07 Open Lot/Corral (Deep Manure Pack) 24.2 21.8 29 10 15 26 89% 0 0 0 0
B 10/04/07 Open Lot Deep Manure Pack 21.0 22.9 41 19 14 33 81% 4 2 0 0
B 03/05/08 Open Lot Deep Manure Pack 9.3 9.2 22 2 6 12 53% 1 0 0 4
B 07/03/08 Open Lot Deep Manure Pack 30.3 28.5 942 62 90 176 19% 17 2 0 17
C 07/03/07 Open Lot/Corral (Deep Manure Pack) 35.2 26.8 141 0 15 26 18% 93 0 0 17
C 06/16/08 Open Lot Deep Manure Pack 37.0 22.8 113 30 23 76 68% 12 3 0
D 10/24/07 Open Lot Deep Manure Pack 16.2 15.1 86 40 36 76 88% 6 3 0 0
D 03/11/08 Open Lot Deep Manure Pack 14.6 12.2 62 8 10 58 93% 1 1 0
D 06/25/08 Open Lot Deep Manure Pack 35.1 24.2 327 54 0 69 21% 18 4 0 2 D 07/26/07 Open Lot/Corral (Deep Manure Pack) 26.3 26.6 220 21 42 85 39% 84 0 0 4
E 06/21/07 Open Lot/Corral (Deep Manure Pack) 33.8 30.2 1,132 2 74 76 7% 517 0 0 537
E 06/21/07 Open Lot/Corral (Deep Manure Pack) 36.0 30.2 1,657 2 87 89 5% 734 0 0 831
E 10/18/07 Open Lot Deep Manure Pack 11.9 10.6 61 9 50 59 97% 1 0 0
E 03/07/08 Open Lot Deep Manure Pack 21.6 19.9 99 13 11 67 68% 8 2 0 5
E 06/10/08 Open Lot Deep Manure Pack 29.7 27.2 129 27 25 82 63% 8 2 0 2
F 04/24/07 Open Lot/Corral (Deep Manure Pack) 17 6 0 6 35% 0 0 0
F 11/08/07 Open Lot Deep Manure Pack 20.0 20.0 57 23 27 51 90% 3 1 0 0
F 03/24/08 Open Lot Deep Manure Pack 16.3 12.2 112 48 16 68 61% 13 1 0 2
F 07/10/08 Open Lot Deep Manure Pack 31.4 29.5 197 32 31 109 56% 16 4 0 5 8

5

0
3

7
0

6

1

3

3
0

4

5

2
0
6

1

5
5

3
0

43Table A6 . Ambient samples taken prior to Ju ly, 2007. Values are concentrations (ppmV for Methane, ppbV for CO and pptV for all others). Samples were to be collected in canisters over a 5 minute per iod after 30 minutes of a consis tent wind direction. Most samples reported did not meet these minimum modeling cr iteria. The number of samples collected for each category is shown in parentheses.

VOC common name mol.wt. Conc. U p w i n d ( 1 9 ) A n i m a l s ( 2 2 ) L a g o o n ( 1 4 ) D i g e s t e r ( 4 ) Methane (ppmv) Methane 16.04 ppmV 6.7 4.3 6.0 186.6 CO (PPBV) Carbon Monoxide 28.01 ppbV 881.8 180.7 453.0 199.0 Methanol (B) Methanol 32.04 pptV 229,649.3 15,298.0 145,152.9 6,612.8 Ethanol (B) Ethanol 46.07 pptV 2,730,499.5 57,571.5 544,337.1 8,333.3 Acetone (MS) Acetone 58.08 pptV 26,759.8 7,497.5 5,260.6 3,162.0 D-Limonene (B) D-Limonene 136.24 pptV 2,209.7 1,378.2 3,033.8 55.0 OCS (MS) Carbonyl Sulfide 60.07 pptV 887.8 610.0 553.1 594.0 DMS (MS) Dimethylsulfide 62.14 pptV 3,280.2 691.4 887.3 1,142.8 CFC-12 (C/D/MS) Dichlorodifluoromethane 120.91 pptV 530.5 547.5 517.2 569.0 CS2 (MS) Carbon Disulfide 76.14 pptV 18.6 42.8 57.7 71.0 CFC-11 (C/D/MS) Trichlorofluoromethane 137.38 pptV 254.1 285.5 252.9 285.8 CFC-113 (MS) Ethane, 1,1,2-trichloro-1,2,2-trifluoro- 187.37 pptV 76.3 84.1 75.9 83.3 CFC-114 (C/MS) 1,2-Dichloro-1,1,2,2-tetrafluoroethane 170.92 pptV 14.1 15.7 14.3 15.5 H-1211 (C/D/MS) hexadecane 226.45 pptV 4.8 5.1 4.9 5.3 HCFC-141b (MS) 1,1-dichloro-1-fluoroethane 116.95 pptV 21.2 28.0 22.3 26.0 HCFC-142b (MS) 1-Chloro-1,1-difluoroethane 100.50 pptV 21.1 23.2 19.3 27.0 HCFC-22 (MS) chlorodifluoromethane 86.47 pptV 308.7 406.6 266.0 489.0 HFC-134a (MS) hafnium carbide 190.50 pptV 75.8 85.2 85.2 76.5 C2Cl4 (C/D/MS) Tetrachloroethylene 165.83 pptV 61.6 62.5 89.6 22.0 C2HCl3 (D/MS) Trichloroethylene 131.39 pptV 4.2 4.5 5.4 5.0 CCl4 (C/MS) Carbon tetrachloride 153.82 pptV 91.3 101.4 93.7 102.8 CH2Br2 (D) Methane, dibromo- 173.83 pptV 0.4 0.4 0.4 0.3 CH2Cl2 (MS) Methylene chloride 84.93 pptV 50.4 77.0 53.6 68.5 CH3 Br (MS) Methyl bromide 94.94 pptV 28.4 29.0 23.7 23.3 CH3CCl3 (C/MS) Ethane, 1,1,1-trichloro- 133.40 pptV 16.9 19.2 16.9 18.5 CH3Cl (MS) Methyl chloride 50.49 pptV 718.2 942.9 832.7 771.0 CH3I (C/MS) Methyl iodide 141.94 pptV 2.1 1.3 2.5 1.0 CHBr3 (C/MS) Methane, tribromo- 252.73 pptV 0.8 1.1 0.9 0.7 CHCl3 (MS) Chloroform 119.38 pptV 20.9 17.4 15.4 16.0 MeONO2 (C/D) Methyl nitrate 77.04 pptV 20.0 6.4 9.9 5.8 EtONO2 (C/D) 92.00 pptV 16.9 3.7 5.3 4.3 i-PrONO2 (C/D) 104.00 pptV 19.1 11.7 18.8 17.6 n-PrONO2 (D) 104.00 pptV 1.8 1.1 1.5 2.0 2-BuONO2 (C/D) 114.00 pptV 10.1 7.2 9.4 9.4 2-PeONO2 (C/D) 124.00 pptV 3.7 3.0 3.3 3.7 3-PeONO2 (C/D) 124.00 pptV 2.8 2.3 2.3 2.9 Propane (B/E) Propane 44.10 pptV 1,658.7 1,292.1 1,798.4 12,603.8 Propene (B/E) Propene 42.08 pptV 192.1 167.2 1,609.4 813.5 Ethane (E) Ethane 30.07 pptV 2,174.7 1,523.5 2,066.9 3,373.0 Ethene (E) Ethene 28.05 pptV 403.4 719.6 2,539.9 2,722.8 Ethyne (E) Acetylene 26.04 pptV 382.9 401.5 383.7 630.5 n-Butane (B/E) Butane 58.12 pptV 162.9 203.6 417.6 233.8 i-Butane (B/E) Isobutane 58.12 pptV 199.2 171.5 509.6 262.8 1,3-Butadiene (B) Butadiene 54.09 pptV 0.6 0.0 0.0 0.0 1-Butene (E) 1-Butene 56.11 pptV 2.1 6.6 5.6 0.0 trans-2-Butene (B) 2-Butene-trans 56.11 pptV 0.7 0.0 0.0 0.0 n-Pentane (E) Pentane 72.15 pptV 120.2 166.3 129.7 152.8 i-Pentane (E) 72.00 pptV 206.7 390.0 292.1 299.5 n-Hexane (B/E/MS) Hexane 86.18 pptV 100.9 290.5 391.5 81.0 Benzene (MS) Benzene 78.11 pptV 86.3 109.7 110.6 97.0 Isoprene (MS) Isoprene 68.12 pptV 150.5 77.2 73.1 58.0 Toluene (MS) pptV 122.9 220.3 161.2 156.3 o-Ethyltoluene (MS) 2-Ethyltoluene 120.19 pptV 34.8 105.0 59.1 7.3 m-Ethyltoluene (MS) 3-Ethyltoluene 120.19 pptV 47.0 157.1 58.4 11.0 Ethylbenzene (MS) Ethyl Benzene 106.17 pptV 118.4 441.9 131.1 54.0 2-Methylpentane (B) 2-Methylpentane 86.18 pptV 136.6 154.8 171.4 77.3 3-Methylpentane (B) 3-Methylpentane 86.18 pptV 119.4 99.1 103.6 12.5 alpha Pinene (MS) alpha Pinene 136.24 pptV 21.7 103.5 25.4 6.5 beta Pinene (MS) beta Pinene 136.24 pptV 4.1 95.3 13.8 6.3 m-Xylene (MS) m-Xylene 106.17 pptV 46.1 152.7 63.1 25.5 p-Xylene (MS) p-Xylene 106.17 pptV 46.0 152.5 63.4 25.0 o-Xylene (MS) o-Xylene 106.17 pptV 16.6 62.4 22.9 6.3 1,2,4-Trimethylbenzene ( M 1,2,4-Trimethylbenzene 120.19 pptV 88.2 314.7 124.4 22.8 1,3,5-Trimethylbenzene ( M 1,3,5-Trimethylbenzene 120.19 pptV 4.2 22.1 9.9 0.0

44

### APPENDIX B

This appendix is the report submitted Octobe r 1, 2007 to CARB for the Year-1 progress report. In order to comply with Task 4, a draft was prepared in April, 2007 and submitted to the project’s advisory group to begin the process of finalizing the Year-2 sampling and analysis program for not only the CARB project but also the other, related monitoring programs for nitrogen compounds, alcohols and feed components. The report is included here in its original form as a reference for the development of the Year-2 monitoring program to collect the dat a used for this final project report.

Data in the figures and tables of appendix B were from the initial year of the project and were superseded by Year-2 data reported above. These data were used primarily to validate various sampling methods and did not include all the field and media blanks collected to correct Year-2 results. While much of the Year-1 results are sufficiently similar to the final results to add credibility to the conclusions, no data from Year-1, reported below, was referred to in the fi nal report nor should it be used to draw conclusions regarding dairy emission rates.

45Progress Report: January 1 to March 31, 2007 (Includes summary of r esults from Year 1)

Dairy Operations: An Evaluation and Comparison of Baseline and Potential Mitigation Practices for Emissions Reductions In the San Joaquin Valley

Principal Investigator:

Dr. Charles Krauter California State Un iversity Fresno

Co-Principal Investigator: Dr. Donald Blake University of California Irvine

California Air Resources Board Contract No. 04-343 Project to be administered as CSU Fresno Foundation Project #37411

The statements and conclusion s in this report are those of the Contractor and not necessarily those of the California Air Re sources Board. The mention of commercial products, their source, or their use in connection with material herein is not to be construed as actual or implied endorsement of such products.

1. Narrative account of project tasks comple ted or partially completed during report period: The activity covered by this c ontract period was primarily fo cused on completing the Year-1 tasks and developing the sampling and analytical program to be used for Year-2 sampling. The primary sampling procedure, as described in the proposal, was the collection of upwind and simultaneous downwind samples at each dairy for each sampling period. The wind conditions required for this canister sampli ng were not present for some of the fall and most of the winter attempts. The problems and proposed changes in the protocol for Year-2 will be discussed in detail below. The additional sampling with flux chambers was very successful and, combined with additional analytical methods supported by the supplemental funding from CSU-ARI, has filled the data gaps in the ambient sampling program very well. In fact, as discussed below, we are proposing to shift the emphasis to the fl ux chamber sampling and continue the ambient sample collection only when the wind conditions are suitable for sampling and modeling of the results.

Summaries of the data collected by both ambi ent and flux chamber sampling and analyzed by Dr. Blake’s lab at UCI as well as the real-tim e monitoring and in-house analysis done at CSU Fresno are attached to this repo rt. A revised Year-2 sampling program is also attached for review prior to discussion with the advisory group and adoption for the early summer sampling period (Task 4). The Year-2 monitoring program (Task 5) is scheduled to start late May, 2007.

2. Problems encountered during repor t period and their resolution: The primary problem encountered during the initial year of field monitoring was the difficulty in collecting upwind and downwind ambient sample s under conditions that would allow modeling

46of the results to calculate flux rates. Minimum wind conditions were initia lly determined to be a wind speed of at least 1 meter/second and a wind direction within 20 degr ees of the mean for a period of at least 2 hours. That proved to be ne arly impossible to achieve except for a few times in April and May. It was part icularly difficult to find during the evening hours and for the dairies located south of Fresno. A revision of the “minimum wind conditions” was devised to reduce the time to 30 minutes at the end of whic h the canisters would be filled over a 5 minute period. It was determined that the upwind samp le air would reach the downwind locations in 5 minutes or less at the minimum wind speed of 1 meter/second so those became the minimal sampling conditions. All the data reported for the ambient sampling in the attached summary was collected under these revised sampling limits. The expense and effort required to analyze a canister made it necessary to limit the sampling to those times when wind conditions would enable the results to be consider ed significant and for modeling to be possible. Less than half of the fall sampling and none of the planned wint er ambient sampling was accomplished because minimal wind conditions were not present. It shou ld be noted that the su ccessful use of the flux chambers and the addition of the INNOVA gas analyz er were being developed at the same time the problems with ambient sampling was occurr ing. It became evident that the flux chamber method would provide more specific source sampling and was not subject to the wind requirements and so was a much better method fo r the systematic sampling of the different dairies for the three seasonal sampling periods.

3. Discussion of work planned before next report: Task 4, the development of a revised Year-2 sa mpling/analysis program and its review by the advisory group will be the next work to be accomplished. A draft of the Year-2 program is attached to this report and a meeting or conference call with the advisory group should occur by early May. If the proposed program is approve d, the first sampling peri od will begin later in May (Task 5). Sampling of the six dairies should be complete by the end of June and the next sampling period will start in September. Additi onal related sampling of land applications, feed supplements, and photosynthetic lagoons will be done at these and other dairies during the time between sampling periods (Task 7). This a dditional work will be supported by supplemental funding from CSU-ARI, USDA and the California Dairy Campaign.

4. Allocation of budget items during report period: An up-to-date accounting of the expe nditures is not currently availabl e. The sub-contract with Dr. Blake at UC Irvine is in place. The Year-1 samples have been analyzed. UC Irvine will bill CSU Fresno for the work to date and it will be included in a billing to ARB in May.

5. Percentage of completion for each task: Tasks 1, 2 and 3 are completed Task 4 is approximately 50% completed Task 5 is approximately 0% completed Task 6 is approximately 0% completed Task 7 is approximately 50% completed

The original proposal, written in early 2005, emphasized the use of samples collected in Summa Canisters taken simultaneously upwind and downwind of significant dairy operations such as the animal housing and lagoon areas. This method ha d been successfully employed in the previous

47study done at two of these six dairies and was exp ected to be an appropriate method if suitable analytical procedures were added. Net incr eases in ROG between the upwind and downwind samples were assumed to be emissions from that dairy operation. Modeling of the sampling results with a Gaussian Plume model would calculate the emissi ons from that operation for the sampling period. The original plan was to samp le for a 2 hour period during the day for two consecutive days and also collect a night sample on one of the two days. This was to be done at each of the six dairies for each of the three sampling periods (May-June, September-October and January-February). This has pr oven to be impossible. Mini mum wind conditions for ambient samples (1 meter/second and a deviation of no mo re than 20 degrees of direction) are rarely present except in the spring and fo r the dairies north of Fresno. The complete set of samples was collected twice out of the planne d 18. Samples were collected fo r 5 minutes rather than 2 hours for most of the spring and summer sampling pe riods but no winter ambient samples were collected because wind conditions never approach ed the minimal levels required for modeling. Additionally, some of the spring samples were the in itial canisters sent down to UCI for analysis. Dr. Blake is in the process of developing a sta ndard gas that should increase the precision of the quantification of these samples considerably. Until that standard is used, the concentrations reported should be considered as relative valu es rather than absolute concentrations.

The complete data set of analysis by the UCI la b of all ambient samples taken in Year-1 is attached as an Excel file titled “Ambient Data UCI Year1”. A summary of net increase for the 17 samples from animal housing, 12 samples from lagoons and 3 samples from the digester at Dairy E are shown on the next page. The list of species has been sorted to place the largest concentrations first. The methane (ppmV), CO (ppbV) and Acetone (pptV) are shown in the table but not included in the total ROG calculatio n. The values shown in the summary table are the average of the net difference (downwind – upw ind) in concentration for each species.

Significant results from this data are: 1. The animal housing areas are a much greater source of ROG than the lagoons. The negative net differences seen for the lagoons will have to be evaluated and modeled on a case by case basis to determine the actual lagoon emission. 2. Alcohols are the primary ROG from animal hous ing. This is confirmed by flux chamber samples summarized below. The average to tal net ROG of 11.6 ppbV for animal housing is 70% Methanol plus Ethanol. The low and negative values for alcohols from lagoon samples may be from contributions to the upwind value from animal housing or feed storage, depending upon the specific dairy.

48Table 1. Summary of Net concentrations of Yea r-1 ambient samples.

Animal Housing Lagoon Digester (Dairy E

Total Average Total Average Total Average

units common name Methane (ppmv) ppmv Methane 17 -3 12 -3 3 243 CO (PPBV) ppbv Carbon Monoxide 17 -415 12 -273 3 5 Ethanol (B) pptv Ethanol 17 2,966 12 -11,557 3 299 Methanol (B) pptv Methanol 17 5,199 12 -1,858 3 3,062 Acetone (MS) pptv Acetone 17 3,545 12 353 3 325 D-Limonene (B) pptv D-Limonene 17 495 12 -600 3 15 DMS (MS) pptv Dimethylsulfide 17 338 12 50 3 76 alpha Pinene (MS) pptv alpha Pinene 17 91 12 -1 3 1 n-Hexane (B/E/MS) pptv Hexane 17 46 12 -13 3 7 Ethane (E) pptv Ethane 17 -23 12 -136 3 259 OCS (MS) pptv Carbonyl Sulfide 17 141 12 63 3 142 2-Methylpentane (B) pptv 2-Methylpentane 17 52 12 4 3 -54 3-Methylpentane (B) pptv 3-Methylpentane 17 -12 12 -58 3 -8 Ethene (E) pptv Ethene 17 166 12 46 3 567 Propane (B/E) pptv Propane 17 -404 12 -634 3 1,549 Propene (B/E) pptv Propene 17 29 12 -6 3 205

CH3Cl (MS) pptv Methyl chloride 17 305 12 95 3 229 Isoprene (MS) pptv Isoprene 17 38 12 -31 3 51 beta Pinene (MS) pptv beta Pinene 17 117 12 14 3 -10

HCFC-22 (MS) pptv chlorodifluoromethane 17 119 12 10 3 -95 CFC-12 (C/D/MS) (PPTV) pptv Dichlorodifluoromethane 17 -2 12 -9 3 10 Ethylbenzene (MS) pptv Ethyl Benzene 17 422 12 16 3 15 CH2Cl2 (MS) pptv Methylene chloride 17 30 12 2 3 10 1,2,4-Trimethylbenzene (MS) pptv 1,2,4-Trimethylbenzene 17 271 12 39 3 -20 Ethyne (E) pptv Acetylene 17 18 12 25 3 46 i-Pentane (E) pptv ? 17 233 12 46 3 -80 CFC-11 (C/D/MS) pptv Trichlorofluoromethane 17 20 12 11 3 13

n-Butane (B/E) pptv Butane 17 38 12 -11 3 9 i-Butane (B/E) pptv Isobutane 17 -16 12 -24 3 -55 MeONO2 (C/D) pptv Methyl nitrate 17 0 12 -1 3 1

n-Pentane (E) pptv Pentane 17 116 12 3 3 16 EtONO2 (C/D) pptv ? 17 -1 12 -1 3 0 m-Ethyltoluene (MS) pptv 3-Ethyltoluene 17 140 12 11 3 -6 Toluene (B/MS) pptv Toluene 17 137 12 35 3 20 i-PrONO2 (C/D) pptv ? 17 0 12 1 3 3

p-Xylene (MS) pptv p-Xylene 17 145 12 20 3 6 m-Xylene (MS) pptv m-Xylene 17 145 12 19 3 6 HFC-134a (MS) pptv hafnium carbide 17 14 12 6 3 -3 CHCl3 (MS) pptv Chloroform 17 2 12 0 3 1 CCl4 (C/MS) pptv Carbon tetrachloride 17 5 12 4 3 4 o-Ethyltoluene (MS) pptv 2-Ethyltoluene 17 87 12 29 3 -13 CS2 (MS) pptv Carbon Disulfide 17 22 12 50 3 65 Benzene (MS) pptv Benzene 17 21 12 9 3 -6 2-BuONO2 (C/D) pptv ? 17 0 12 0 3 0

CFC-113 (MS) pptv t hane, 1,1,2-trichloro-1,2,2-trifluor o 17 3 12 3 3 1 C2Cl4 (C/D/MS) pptv Tetrachloroethylene 17 15 12 13 3 9

o-Xylene (MS) pptv o-Xylene 17 60 12 5 3 -1 HCFC-141b (MS) pptv 1,1-dichloro-1-fluoroethane 17 6 12 1 3 1 HCFC-142b (MS) pptv 1-Chloro-1,1-difluoroethane 17 1 12 1 3 -10 1,3,5-Trimethylbenzene (MS) pptv 1,3,5-Trimethylbenzene 17 23 12 6 3 0 CH3 Br (MS) pptv Methyl bromide 17 -1 12 2 3 2 C2HCl3 (D/MS) pptv Trichloroethylene 17 1 12 1 3 1 CH3CCl3 (C/MS) pptv Ethane, 1,1,1-trichloro- 17 2 12 0 3 0 CH3I (C/MS) pptv Methyl iodide 17 0 12 0 3 0 CFC-114 (C/MS) pptv 2-Dichloro-1,1,2,2-tetrafluoroetha n 17 1 12 1 3 0

n-PrONO2 (D) pptv ? 17 0 12 0 3 0

1-Butene (E) pptv 1-Butene 17 4 12 2 3 0 trans-2-Butene (B) pptv 2-Butene-trans 17 1 12 -1 3 0

2-PeONO2 (C/D) pptv ? 17 0 12 0 3 0 H-1211 (C/D/MS) pptv hexadecane 17 0 12 0 3 0 3-PeONO2 (C/D) pptv ? 17 0 12 0 3 0 cis-2-Butene (B) pptv 2-Butene-cis 17 0 12 0 3 0 1,3-Butadiene (B) pptv Butadiene 17 -1 12 0 3 -4 CH2Br2 (D) pptv Methane, dibromo- 17 0 12 0 3 0 CHBr3 (C/MS) pptv Methane, tribromo- 17 0 12 0 3 0

11,630 -14,298 6,333

Ethanol % of ROG 26% 5% Methanol % of ROG 45% 48% Total Alcohol % of ROG 70% 53%

49Flux Chamber Data Summary The use of the EPA Isolation Flux Chamber had not been adopted by our research group when this project was initially propose d. We had observed its use by Dr . Chuck Schmidt at two of the dairies in this study and we expected to de velop the method as an additional monitoring technique with supplemental funding from CSU- ARI. The difficulties encountered with the ambient sampling provided a str ong inducement to develop the flux chambers as an alternative that would both eliminate the pr oblem of the minimum wind requi rement and enable much more specific monitoring of different sources with in the components of the dairy operation. The method has been very successful with respect to both of those goals. There is a US-EPA Protocol for the Isolation Flux Chamber that has been published and used by a number of researchers. We used the pub lished protocol without modifica tion for the sampling described below.

Unlike the ambient, upwind/downwind sampling wh ere the dairy could only be differentiated into major components such as the animal hous ing and lagoon systems; sampling with the flux chambers enables very specific areas to be is olated and sampled wit hout interference or contamination from other, nearby sources. We have developed a monitoring program with the flux chambers that has proven to be effective in the last two sampling periods and will be proposed as the primary method for the Year-2 pr otocol. The flux chambers have nearly the opposite problem compared to the ambient canister samples. The flux chamber is limited to the 0.5M 2 area that it covers and the sampling peri od is limited to about 30 minutes following the 30 minute flush/preparation time. Replication of th e flux chamber data is therefore necessary. At least 2 chambers are used for each measurement and 4 will sometimes be required when variability is expected to be high. We currently have 4 chambers with an additional 4 on order. That should be sufficient for the prop osed Year-2 monitoring program.

The ability to sample more discrete locations within the dairy has already shown the flux chambers to be an ideal method for work such as this. The initial di scovery that alcohols, particularly ethanol, are the dominant ROG in many samples led us to suspect the silage and feed as possible significant sources. Flux chambers we re used to monitor those components as well as fresh manure on the flush lanes, the manure p ack on the exercise corrals and some monitoring of solids and effluent applications to crop land. The emerging importance of ethanol and methanol created the need to monitor those ROG’ s more frequently and at less cost than the canister samples that required GC-MS analysis either at UCI or in-house. A photo-acoustic, multi-gas analyzer was purchased to monitor N 2 O and NH 3 from the flux chambers at the six dairies for the Denitrification/Decomposition proj ect in collaboration w ith Bill Salas at New Hampshire. This INNOVA has the capability to monitor six gasses in real time at sub-ppb concentrations. We had the INNOVA configured for ethanol and methanol along with the CO 2 , water vapor, N 2 O and NH 3 needed for the UNH project. The INNOVA data for the alcohols was very consistent when compared to the analysis of a canister taken at the same time and analyzed at UCI or in-house. The real-time INNOVA values for silage were consistently 3-4 times greater than the UCI analysis of a canister from the same flux chamber (see Table 2). Dr. Blake as well as others collaborating on the project have questioned the ability of the GC-MS system to extract all of the water soluble gasses such as these alcohols from the canisters when they are analyzed. There is the possibility that et hanol and methanol values from canister analysis are reduced by this sampling problem and so the higher INNOVA m easurements may, in fact be more accurate.

50In addition to canisters sampled from the flux chamber for GC-MS analysis and the INNOVA monitoring that is done at the same time, NH 3 is also monitored with a denuder and we have recently been sampling with sorbent tubes for VFA analysis. The VFA data is not yet available but the method will be used in the Year-2 program if it proves to be effective.

The components of the dairy operations for whic h flux chambers were used are silage, feed (Total Mixed Ration or TMR), ex ercise corrals, and fl ush lanes on a regular basis beginning with the fall-’06 sampling period. Some data is avai lable from summer-’06 for these sources as well as others such as feed supplements, solids storag e, and land applications. The flux chambers are being adapted to float on lagoons but no work ot her than method development has been done to date. A summary of the data from canister sampling in the flux chambers and a comparison with INNOVA data taken at the same time is show n below for silage, TMR, exercise corrals and flush lanes. This is only a small amount of the INNOVA data since only those measurements that coincided with canister samples are repor ted here. Additional INNOVA data is shown where it is needed to support the results for this project.

Silage The most likely source of ethanol at a dairy was expected to be th e silage pile where it would be produced by yeast fermentation of the plant materi al as part of the ensiling process. Flux chambers were placed at the face of the pile wh ere it is exposed for the feed mixing operation. No monitoring of the larger, covered portion of the silage pile has been done to date. Both the undisturbed face of the pile and the loose silage disturbed by the feed mixing equipment were sampled with the flux chambers. Canisters were used to sample from the flux chamber and analyzed at both UCI and CSUF. The INNOVA gas analyzer samp led and reported the alcohols in real-time from the chambers. Three INNOVA samples of one minute each were analyzed and recorded either just before or just after th e canister sample was taken. Both samples were completed within the same 10 mi nute period. The averages of the 8 canisters analyzed at UCI are shown in Table 2. The INNOVA unit became av ailable in late June and was matched with five of the canister samples, also shown in Tabl e 2. The complete data set can be found in the Excel file titled “Year 1 Flux Chamber data”.

Table 2. Summary of total ROG and al cohol fluxes in silage samples. Silage Emission Rate ( μ g/m 2 /min) 5 INNOVA samples with 8 UCI canisters Summary and Comparison of UCI Canisters with INNOVA data UCI Canister Ethanol μ g / m 2 / min. 14,897 UCI Canister Methanol μ g / m 2 / min. 695 INNOVA Ethanol μ g / m 2 / min. 60,598 INNOVA Methanol μ g / m 2 / min. 12,892 INNOVA/UCI Ethanol ratio 5.14 INNOVA/UCI Methanol ratio 11.53 Total VOC's (UCI) μ g / m 2 / min. 16,303 Total ROG (UCI) μ g / m 2 / min.* 15,783 Ethanol % 87.8% Methanol % 9.2% Total Alcohol % 97.0%

*Total ROG's = UCI total VOC - (methane+CO+Acetone)

51The alcohols, ethanol and methanol , were nearly all of the ROG m easured from the silage. They were 97% of the total measured by the canister analysis. Etha nol concentrations were the dominant ROG at about 10 times the methanol levels. The INNOVA measured the alcohols at higher concentrations than the UCI canister analysis. There was one anomalous ethanol value and one methanol flier from the INNOVA. If th ose are removed from the average ratios, the INNOVA/Canister ratio is cons istently between 3 and 4 for both alcohols. The INNOVA was returned for recalibration of the alcohol channels late in the summer and the data from the unit following that was much more consistent. Furt her comparisons between canister analysis and INNOVA data will be available in Year-2. The development of a standard at UCI to improve the quantification of those an alyses will increase the validity of the comparison.

The contribution of silage to Ethanol emissions fr om dairies was rather va riable as shown in the data files and summarized in Fi gure 1 below. The data in Fi g. 1 is from the INNOVA and includes those values from Table 2 along with others taken when no canister sample was collected.

Figure 1. Ethanol flux rates from silage piles mon itored at the six dairies from April to November, 2006. Each value is the average of 3 measurements taken within a 4 minute period.

Ethanol Fluxes from Silage Pile Face

0 20000 40000 60000 80000 100000 120000

F F F F C C B A D D E E Dairyug/m2/min Ethanol

The considerable variability could be due to a nu mber of factors. Some silage is made from corn, including the grain, while other silage is ma de from grass and winter grown cereals with a lower carbohydrate content that s hould produce less ethanol. A mo re interesting variable from the point of view of potential mitig ation is the density of the silage pile as a result of the amount of compaction during its construc tion. Ethanol production from yeast fermentation is a symptom of low quality silage. Good silage is made when the plant material is compacted to the point where no oxygen is present and lactic acid bacter ia are the predominant microbe. Lactic acid formation reduces the pH of the silage and preser ves it. Incomplete compaction allows sufficient oxygen into the silage for yeast to exist and ferment carbohydrates to ethanol. The density of the silage piles monitored by the flux chambers was measured by taking a core according to a published method and weighing it. The resul ting densities are shown in Table 3.

52Table 3. Silage density of piles mon itored at the six di aries during 2006.

Dairy Date A vg. DM Denstiy CSUF 3/24/2006 18.7 CSUF 4/7/2006 11.2 A 4/10/2006 17.9 A 4/13/2006 15.1 A 4/24/2006 16.9 A 9/26/2006 11.1 B 7/10/2006 14.1 B 9/6/2006 9.3 C 1/11/2007 11.3 C 8/8/2006 6.2 D 6/1/2006 14.1 D 11/14/2006 12.2 E 6/23/2006 9.9 F 7/24/2006 8.6

The high ethanol fluxes in Fig. 1 for the sila ge at dairy C was measured on August 8 and corresponds to the lowest density (6.2) of all the m easured silage. The high ethanol found at dairy F was measured on July 24, matching the next lowest silage density ( 8.6). It appears that high ethanol fluxes from silage are linked to low density silage. The density of silage recommended by UC is 12 to 15. The ethanol fluxes from silage in that range were much lower, presumably because the yeast fermentation was reduced by the more anaerobic conditions. The monitoring of ethanol and comparison with silage density will be continued at each dairy in Year-2.

Total Mixed Ration (Feed) The feed is a mixture of various components fo rmulated to provide th e proper amount of energy and nutrition to the various groups of animals at the dairy. The solid and liquid components are loaded into a large bin on a truck or trailer wh ere they are mechanically mixed and delivered to the animals through a chute while the feed wagon is driven along the feed lane. This operation typically takes place two or three times each day and the Total Mixed Ration (TMR) is consumed by the cows in about a 6 hour period. Silage is usually the la rgest component of the TMR so significant ethanol fluxes might also be expected from the feeding operation. Since the feed is spread over a much larger area than that of the silage pile face, the potential for emissions is greater.

The fluxes from the TMR were monitored by plac ing chambers on the feed as soon as it was delivered to the animals. The emission of etha nol was expected to change as the feed was consumed and as the initial volatile ROG rapidl y vaporized. A second set of flux chambers was placed on the feed after an hour to monitor any change in emissions with time. The flux chambers must be flushed with zero air for 30 minutes before sampling or measurements are taken according to the US-EPA published protocol so the values reported are for 30 minutes and

5390 minutes after feeding. The average of 18 canisters collected betw een May and November, 2006 are shown along with 12 corresponding INNOVA samples in Table 4.

Table 4. Summary of total ROG and alc ohol fluxes in feed (TMR) samples.

FEED Emission Rate ( μ g/m 2 /min) 12 INNOVA samples with 18 UCI canisters Summary and Comparison of UCI Canisters with INNOVA data UCI Canister Ethanol μ g / m 2 / min. 5,194 UCI Canister Methanol μ g / m 2 / min. 764 INNOVA Ethanol μ g / m 2 / min. 23,697 INNOVA Methanol μ g / m 2 / min. 2,922 INNOVA/UCI Ethanol ratio 3.98 INNOVA/UCI Methanol ratio 3.73 Total VOC's (UCI) μ g / m 2 / min. 6,671 Total ROG (UCI) μ g / m 2 / min.* 6,211 Ethanol % 82.8% Methanol % 16.2% Total Alcohol % 99.0%

*Total ROG's = UCI total VOC - (methane+CO+Acetone)

Alcohols are the dominant ROG in the TMR as they were in silage. The flux rates are lower since not all the components ar e subject to fermentation. The higher moisture content of the TMR compared to silage may also be a factor if the soluble alcohols are being trapped in water. The ethanol:methanol ratio is somewhat lower than in silage as well. The ratio of the INNOVA data to the canister samples is even mo re consistent than it was for silage.

A comparison of the initial TMR emissions meas ured at 30 minutes to those measured at 90 minutes (Fig. 2) shows a consider able decrease in volatile ethanol over time. The flux of ethanol appears to decrease by nearly ha lf from the initial hour to the second hour. A few samples have been taken over a longer period of time. Those indicate this decrease in alcohol flux continues through the several hours that the TMR is in place.

The third significant ROG found in the TMR samp les after ethanol and methanol was limonene. It was found at concentrations of about 10% of the methanol flux at dairies A, C and E, at times. Dairy A frequently uses citrus pulp as a co mponent of their TMR and the other dairies occasionally do the same. The presence of limonene in the TMR was always correlated with the use of citrus pulp as a supplement.

Flush Lanes and Fresh Manure

Flux chambers were used on the surface of the fl ush lanes to monitor emissions from both the fresh manure as it is deposited when the anim als are feeding and the flushed lanes when the manure had been removed to the lagoon system. The highest fluxes were expected to be just prior to flushing and that appears to be the case. Flux chambers were used 8 times on 5 of the dairies to monitor the pre-flush fluxes in th e summer and fall of 2006. The dominant ROG is ethanol, followed by methanol as it was for the feed and silage. The presence of limonene that was correlated with citrus pulp in the TMR also o ccurred as a flux from the fresh manure at some of those same times. The magnitude of the ROG flux from the fresh manure is less than 10% of that measured for the feed but the area of the fl ush lane is considerably larger so they may be

54similar with respect to actual emissions. Th e sampling program in Year-2 will include flux chamber monitoring at several intervals to charact erize the changes in flux from the clean lanes to the heaviest manure load just prior to flushing.

Table 5. Summary of total ROG and alcohol fluxes in fresh manure samples.

Flush Lane (Pre Flush) Emission Rate ( μ g/m 2 /min) 8 UCI canisters Summary Comparison of UCI Canisters UCI Canister Ethanol μ g / m 2 / min. 265 UCI Canister Methanol μ g / m 2 / min. 43 Total VOC's (UCI) μ g / m 2 / mi n Total Alcohol % 541 Total ROG's* 317 Ethanol % 76.5% Methanol % 15.5% Total Alcohol % 92.1% Methane % of VOC's 41.4%

*Total ROG's = UCI total VOC - (methane+CO+Acetone)

The range of flux values for these samples runs from a low of 12 mg/M 2 /min. to nearly 800. The wide variation may be due to amount or age of th e manure or some other factor at the dairy. The full data set can be found in the Excel file titled “Year 1 Flux Chamber data”.

Exercise Corrals The open areas next to the free stalls are used by the cows in good weather for exercise and bovine socializing. After the flus h lanes, these exercise pens co llect the most manure and are a potential emission source. Flux chambers were set up on several of thes e corrals to monitor emissions from the manure pack during the summer and fall of 2006. Data from 3 canisters collected from those chambers and analyzed at UCI are summarized below. The full data set may be found in the Excel file title d “Year 1 Flux Chamber data”.

Table 6. Summary of Total ROG and alcohols in exercise corral samples.

Corrals Emission Rate ( μ g/m 2 /min) 3 INNOVA samples with 3 UCI canisters Summary and Comparison of UCI Canisters with INNOVA data UCI Canister Ethanol μ g / m 2 /min. 12.4 UCI Canister Methanol μ g / m 2 /min. 13.6 Total VOC's (UCI) μ g / m 2 / min. 305 Total ROG (UCI) μ g / m 2 / min.* 29 Ethanol % 42.6% Methanol % 47.0% Total Alcohol % 89.6% Methane % of VOC 38.8%

*Total ROG's = UCI total VOC - (methane+CO+Acetone)

55Fluxes of ROG from the surface of the exercise co rrals are considerably lower than those from TMR, silage or fresh manure but it is still pot entially significant because of the large area involved. The limited number of samples analyzed to date does not allow conclusions to be drawn but it can be pointed out that the alcohols are still the dominant ROG. The ROG is a much smaller fraction of the total VOC pr imarily because the methane and CO were proportionally higher in 2 of these 3 samples. Th e regular sampling of the corrals at each dairy in each sampling season proposed for the Year-2 program should provide sufficient data to estimate emission fluxes from the corrals.

Additional sampling and analysis These same six diaries are used for related projects to investigate a number of additional air and water quality parameters. The sampling periods are generally similar except for the land application monitoring and other practices that do not occur on a regular basis. The sampling and analysis for those relate d projects are included in th e Year-2 sampling program.

Year-2 Sampling Program Task 4 of the project calls for the development of a sampling and analysis program to monitor the six dairies in the second year of the study. Th is Year-2 program is to be developed from the initial monitoring program used in Year-1. Th e field sampling methods, analytical procedures and schedule to be followed in Year-2 will be ad opted after a review of the Year-1 results and consultation with the designated advisory group a nd ARB staff. This proposed Year-2 program is, therefore subject to revisi on until it is adopted for the summer-07 sampling period.

Sampling schedule: In order to characterize volatile organic compou nd emissions from San Joaquin Valley dairies a total of six dairies were selected for their di ffering manure management st yles as well as to provide a sense of facility variability of emissions. The six dairies are to be sampled three times per year to evaluate season emission charac teristics. These periods chosen were: 1. Winter (December to March) 2. Summer (May to July) 3. Late Summer/Fall (September to November) Field sampling methods: Two methods of emissions monito ring are used in the project: 1. Upwind/Downwind ambient sampling utilized a dispersion model (IS C st3) to derive emission fluxes. 2. USEPA Emission Isolation Flux Chamber used according to the published protocol for monitoring fluxes from surfaces. 1. The upwind/downwind method is not a disc rete sampling method and can only break down emission sources into two categories on the dairy f acility. The method also requires a consistent wind speed and direction for pr oper modeling conditions. The fo llowing samples will be taken when wind conditions are present to enable modeling of the results: When minimum wind conditions are not present, these samples will not be collected. Additional flux chamber samples may be taken in place of the ambient samples. 1. Animal Housing

a. Free Stalls b. Open Lot/Corrals

562. Lagoon Systems

a. Treatment Lagoons b. Storage Ponds When minimum wind conditions are not present, these samples will not be collected. Additional flux chamber samples may be taken in place of the ambient samples. 2. Use of the flux chamber method provides the capability to discrete ly sample individual sources within the animal housing area. Four so urces were chosen to sample from the animal housing: 1. Total Mixed Ration

a. 0.5 to 1 hour post feeding b. 1.5 to 2 hours post feeding 2. Flush Lane

a. Pre-Flush (Pre-Scrape, Pre-Vacuum) b. Post-Flush (Post-Scrape, Post-Vacuum) 3. Bedding 4. Open Lot/Corral

a. Deep Manure Pack b. Shallow Manure Pack

c. Harrowed Manure Pack (when available) 5. Silage Pile Face

a. Disturbed 6. Wet Distillers Grain (currently fed at 2 of 6 dairies) or other significant feed components Analytical Methods

1. UC Irvine - Gas Chromatogra phy/MS, ECD, FID Detectors

a. Sample Media = 2L canisters b. Number of Compounds Quantified = 64 2. CSUF – Gas Chromatography/MS (TO-15 and PAMS)

a. Sample Media = 6L summa-type b. Number of Compounds Quantified i. TO-15 =62 ii. PAMS (Photochemical Assessment Monitoring Stations) = 57 3. INNOVA 1412 Photoacoustic Field Gas Analyzer (1 st unit in use since August, ’06)

a. Ammonia b. Ethanol

c. Methanol d. Carbon Dioxide

e. Nitrous Oxide 4. INNOVA 1412 Photoacoustic Field Gas Anal yzer (2nd unit ordered April, ’07)

a. Methane b. Trimethylamine

c. Total Hydrocarbons as Propane d. Acetic Acid

e. Propanol 5. EAS Lab Inc. TO-17 Volatile Organic Acids from Sorbent Tube

a. Sample Media - Sorbent Tube b. Number of Compounds Quantified = 5

57Emission Source Analysis Silage and total mixed ration samples are co llected from chamber locations immediately following emissions monitoring, placed into a pl astic bag, and stored in a sample cooler. Samples are given specific sample numbers, logged into a log sheet, and prepared for shipment to the analytical laboratory. An alysis of feed samples are provided by Dairyland Laboratories Inc. (Arcadia, WI) who performs a commercia lly available analysis called a Fermentation Quality Analysis or VFA Profile. This analys is measures the following parameters on a dry matter basis. 1. Moisture (%) 2. Dry Matter (%) 3. pH 4. Lactic Acid (%) 5. Acetic Acid (%) 6. Propionic Acid (%) 7. Butyric Acid (%) 8. Iso-Butyric Acid (%) 9. Ethanol (%) 10. Methanol (%) 11. Crude Protein (%) 12. Ammonia-N (% of crude protein) 13. Total Acids (%) Manure samples are collected from chambers locations immediately following emissions monitoring, placed into a plastic bag, and stored in a sample c ooler. Samples transported to CSUF lab facilities and stored until delivery to an analytical laboratory. Manure samples are analyzed for the following: 1. Total Nitrogen 2. Ammonium (NH 4 -N) 3. Nitrate (NO 3 -N) 4. Organic Matter (%)

58Sampling Program: Year-1 The sampling program in Year-1 was develope d from spring-06 through the winter-07 sampling periods. The initial, ambient sampling was s upplemented by the flux chambers, CSUF canister sampling and INNOVA monitoring as additional funding became available. The sampling shown in Table 7 is the final program as it was developed for the winter ’06 period.

Table 7.

Source UC Irvine CSUF Innova 1412 Total Ambient Upwind - 2 day & 1 night 3 3 6 Ambient Downwind Housing - 2 day & 1 night 3 3 6 Ambient Downwind Lagoon - 2 day & 1 night 3 3 6 Total Mixed Ration (0.5 - 1 h post) 1 1 2 4 Total Mixed Ration (1.5 - 2 h post) 1 1 2 4 Silage Pile Face (Disturbed) 1 1 2 4 Flush Lane (Pre-Flush) 1 1 2 4 Flush Lane (Post-Flush) 1 2 3 Bedding 1 2 3 Open Lot/Corral (Deep Manure Pack) 1 1 2 4 Open Lot/Corral (Shallow Manure Pack or Harrowed) 11 2 4 Field Blank 1 1 1 3 Field Replicate 2 2 6 10 Totals 18 20 23 61 Sampling Program - Year 1 Analytical Method

Samples are from flux chambers except for those designated as “Ambient”

In addition to the dairy sampling program shown in Table 7, land applicat ion of liquid effluent and solids were also monitored for ROG and various N emissions. Lagoon sampling with the flux chambers is under development and will be included for selected sites in the Year-2
program.

59Sampling Program: Year-2 The sampling and analysis program proposed fo r Year-2 will begin with the summer-07 sampling period and will be maintained in this form throughout the year. Additional sampling and analysis may be added and a Year-3 program will be developed for the ARI and USDA funded portions of the project through 2009.

Table 8.

Source UC Irvine CSUF TO-17 Innova 1412 Total Ambient Upwind - 1 & 1 (when possible) 2 2 4 Ambient Downwind Housing - 1 day & 1 night 2 2 4 Ambient Downwind Lagoon - 1 day & 1 night 2 2 4 Total Mixed Ration (0.5 - 1 h post) 1 1 1 2 5 Total Mixed Ration (1.5 - 2 h post) 1 1 1 2 5 Silage Pile Face (Disturbed) 1 1 1 2 5 Flush Lane (Pre-Flush) 1 1 1 2 5 Flush Lane (Post-Flush) 1 2 3 Bedding 1 2 3 Open Lot/Corral (Deep Manure Pack) 1 1 1 2 5 Open Lot/Corral (Shallow Manure Pack or Harrowed) 11 1 2 Field Blank 1 1 1 1 4 Field Replicate 2 2 1 6 11 Totals 15 17 8 23 63 Proposed Sampling Program - Year 2 Analytical Method

5

Samples are from flux chambers except for those designated as “Ambient”
In addition to the proposed dairy sampling progra m shown in Table 8, land application of liquid effluent and solids will also monitored for R OG and various N emissions when the opportunity arises. Solids applications in the winter and spring as well as effluent irrigations in the spring and summer will be monitored on at least half of th e dairies, if possible. Canisters designated for ambient sampling that cannot be used due to insufficient wind will be employed for additional flux chamber samples of silage, TMR, flush lanes, lagoons and land applications. Lagoon sampling with the flux chambers at selected site s will be added for the CDC project and included in the Year-2 program.

60

### APPENDIX C

Appendix C is a description of the analytical systems and procedures provided by Dr. Donald Blake in the Department of Chemistry at UC Irvine. This contract from CARB specified the use of Dr. Blake and this l aboratory for the analysis of samples collected by CSU Fresno field staff for the study. This document was orig inally part of the proposal and is included here for the det ails of the analytical processes.

61

### Organics Analysis – Detailed Description

Responsibilities Dr. Donald Blake and his UC Irvine team will anal yze project test canisters collected at dairies for analysis of methane, carbon monoxide, selected C 2 -C 10 nonmethane hydrocarbons, selected C 1 -C 2 halocarbons, C 1 -C 5 alkyl nitrates, and selected sulfur gases. Canisters will be assayed within 2 wee ks of their being received and preliminary data will be transmitt ed to the PI within 2 2 weeks after the sample analysis is complete. A detailed description of the anal ytical methods to be used for the project is described below.

Reports, Data and Other Deliverables Prepare monthly progress reports to CSU Fresno that will in clude QA/QC checked and flagged data in spreadsheet format.

Experimental Setup

A 1215 cm 3 sample aliquot (standard temperatur e and pressure) from an individual canister is introduced into the system mani fold and passed over glass beads maintained at liquid nitrogen temperature. The flow is regulated by a Brooks Instrument mass flow controller model 5850E, and is kept below 500 cm 3 /min to ensure complete trapping of the relevant components. This procedure ha s the effect of pre-concentrating the relatively less-volatile components of the sample (such as halocarbons and hydrocarbons) while allowing vo latile components (such as N 2 , O 2 , and Ar) to be pumped away. The less volatile compounds ar e then re-volatilized, by immersing the loop containing the beads in hot water ( 80°C), and subsequently flushed into an helium carrier flow (head pressure 48 psi). This sample flow is then split into six streams. Each stream is chromatographically separated on an individual column and detected by a single detector. Three HP 6890s form the co re of the analytical system. Electroncapture detectors (ECD, sensitive to halocar bons and alkyl nitrates), flame-ionization detectors (FID, sensitive to hydrocarbons), and a quadrupole mass spectrometer (MS, for unambiguous compound identification and selected ion monitoring) will be employed.

The first HP-6890 (GC-1) contains two columns. The first column is a J&W DB-5 (30 m, I.D. 0.25 mm, film 1 mm) connected to a Restek 1701 (5 m, I.D. 0.25 mm, film 0.5 mm), which is outputted to an ECD detector. The second column is a DB-5ms (60 m, I.D. 0.25 mm, film 0.5 mm), which is outputt ed to an MS detector (HP-5973). The DB5/Restek 1701 receives 7.2% of the total ca rrier flow, and the DB-5ms receives 10.1%. The second HP-6890 (GC-2) contains two colu mns. The first is a J&W DB-1 column (60 m, I.D. 0.32 mm, film 1 mm) output to an FID detector. This column receives 14.7% of the flow. The second is a J&W Cyclodex (60 m, I.D. 0.32 mm, film 0.5 mm) receives 10.8% of the flow and is plumbed to an FID. The third HP-6890 (GC- 3) contains a J&W GS-Alumina PLOT column (30 m, I.D. 0.53 mm) connected to a DB-1 (5 m, I.D. 0.53 mm, film 1 mm), which is output to an FID det ector, and a Restek 1701 (60 m, I.D. 0.25

62mm, film 0.50 mm), which is output to an E CD detector. The GS-Alumina PLOT column receives 49.9% of the flow, and the Restek 1701 receives the remaining 7.3%. Output from each detector is recorded digitally us ing Chromeleon software (Spectra Physics, San Jose, CA). Each resulting chromat ogram will be manually modified, and each peak shape individually checked. This type of quality control is very important for datasets of this size because a slight change in retent ion time or peak shape can cause We at UC Irvine generate our own zero-air and nitr ogen for use in our FID and ECD detectors. House air is passed through a CUNO Inc. model AP101T aqua pure water filter filled with glass wool, then through a Whatman 64-02 Air Dryer equipped with a 100-12 BX prefilter. This removes oil, wa ter, and particulates from the air stream, which is then split and directed into a Domnick Hunter nitr ox-nitrogen generator (N G7-0) and a Praxair zero-air generator (model Airlab WHA 76803). The output from these devices are split further and directed into gas regulators for head pressure r egulation. Before entering our system all gases employed are pass ed through homemade graphite/molecular sieve traps to remove any remaining c ontaminants. These traps are preconditioned (and regenerated) by flowing gas thr ough them at a te mperature of 350  ̊ C for at least 5 hours. The three FIDs operate at a detector temperature of 250  ̊ C with a zero-air flow of 450 mL/min, an H 2(g) flow of 40 mL/min, and a detecto r makeup gas flow of 20 mL/min N 2(g) . The ECDs detector temperatures are 250  ̊ C with a detector makeup flow of 50 mL/min N 2(g) . The relative flow passing through an individu al column depends primarily on its inner diameter. At UC Irvine we split the flow among the channels in such a way as to facilitate detection of a vari ety of halo- and hydrocarbon s pecies. The majority of the flow is directed to the PLOT column due in part to the lower per-molecule sensitivity of the FID detector, and the low ambient concentrations of many non-methane hydrocarbons in remote regions. The split ra tios are found to be highly reproducible as long as the specific humidity of the injected air is above 2 g-H 2 O/kg-air. For this reason (as well as to increase the stability of cert ain compounds in the canisters) 20 torr of water is added to each (preconditioned, evacuat ed) canister before being sent into the field. Multiple standards will be employed during the 8 week period of sample analysis. Working standards will be run roughly ev ery two hours, and absolute standards will be run at least twice daily. Our lab regularly co llects and calibrates pressurized cylinders of air from different environments for use as working standards. A primary reference standard for halocarbons was previously calibr ated from static dilutions of standards prepared in this lab. Its absolute accura cy is tied to a manomet er measurement and how accurately the appropriate volume ratios for the dilution line used are known. At UC Irvine we also have pr imary halocarbon standards pr ovided by other research groups involved in halocarbon analysis. For hydrocarbons, we use a propane standard pur chased from the National Bureau of Standards (SRM 1660A) to calculate a Pe r-Carbon-Response-Factor (PCRF) for the FIDs. This is compared to PCRFs calculated from more readily available commercial standards to check the absolute accuracy of the commercial standard, as well as the appropriateness of using the same PCRF fo r different compounds. From analysis of the commercial standard we assign a different PCRF for each alkane, from ethane to

63octane. This PCRF is then used for any compound with an equi valent number of carbons. For example, the PCRF det ermined for butane is employed during quantification of the butenes . We have cross-checked our calibration scheme against absolute standards from other groups fo r both hydrocarbons and halocarbons. Additionally, we participate in the Non-Methane Hydrocarbon Intercomparison Experiment (NOMHICE). The results of this experiment demonstrate that our analytical procedures consistently yield accurate identification of a wide range of unknown hydrocarbons and produce exce llent quantitative results. We estimate our typical absolute accuracy as 2-10%, increasing as we approach our detection limits. At UC Irvine, our analytical accuracy ranges from 2 to 20%. The precision of the measurements varies by compound and by mixi ng ratio. For example, the measurement precision is 1% or 1.5 pptv (w hichever is larger) for the alkanes and alkynes, and 3% or 3 pptv (whichever is larger) for the alkenes. The precision for C 2 Cl 4 at 5 pptv is ±0.05 pptv. The limit of detection (L OD) is 3 pptv for all NMHCs. Typical alkyl nitrate detection limits are 0. 03 pptv (0.03 pptv for methyl nitrate) and precision ±5% at mixing ratios above 5 pptv and ±10% below 5 pptv. The detection limits for methyl iodide (CH 3 I), bromoform (CHBr 3 ) and DMS are 0.02, 0.02, and 1 pptv, respectively. Precision values of 1 and 2%, respectively for CH 3 I and CHBr 3 are typical. For DMS, the precision is approximately 3% at mixing ratios >25 pptv, and 1 pptv or 15%, whichever is higher, at mixing ratios <10 pptv.
We have been involved in numerous NASA and NSF airborne projects during which more than twenty-five thousand samples have been collected and assayed for a wide range of hydrocarbons and halocarbons. Once samples are assayed, the stored chromatograms are individually inspected the reports from thos e chromatograms are then summarized in spreadsheet format and che cked for inconsistencies. Once the quality control is complete t he data are ready for archive.

At UC Irvine we will quantify the gases using our 6 column/6 detector analytical system. The table on the next page lists the gases that are usually quantified and the associated limits of detections (LODs). Additional gases can be added if necessary.

64

### Gases Usually Quantified at UC Ir vine by Dr. Donald Blake

Gas LOD (ppt) Gas LOD (ppt) Ethane 3 DMS 1 Ethene 3 OCS 50 Ehtylene 3 Methyl Nitrate 0.03 Propane 3 Ethyl Nitrate 0.03 Propene 3 n-Propyl Nitrate 0.03 n-Butane 3 i-Propyl Nitrate 0.03 i-Butane 3 2-Butyl Nitrate 0.03 1-Butene 3 2-Pentyl Nitrate 0.03 cis-2-Butene 3 3-Pentyl Nitrate 0.03 trans-2-Butene 3 CH2FCF3 (HFC-134a) 1 1,3-Butadiene 3 CH3CCl2F (HCFC-141b) 1 n-Pentene 3 CH3CClF2 (HCFC-142b) 1 i-Pentene 3 CHClF2 (HCFC-22) 1 Isoprene 3 CBrClF2 (H-1211) 0.05 n-Hexane 3 Acetone 50 2-Methylpentane 3 CCl3F (CFC-11) 1 3-Methylpentane 3 CCl2F2 (CFC-12) 10 Benzene 3 CCl2FCClF2 (CFC-113) 1 Toluene 3 CClF2CClF2 (CFC-114) 1 o-Ethyltoluene 3 CH3Cl 10 m-Ethyltoluene 3 CCl4 0.1 1,2,4-Trimethylbenzene 3 CH3CCl3 1 1,3,5-Trimethylbenzene 3 CHClCCl2 0.05 o-Xylene 3 CH3Br 1 m-Xylene 3 CH2Br2 0.02 p-Xylene 3 CHBr3 0.02 Ethylbenzene 3 CH3I 0.02 a-Pinene 3 CH2Cl2 0.2 b-Pinene 3 CCl2CCl2 0.1

65

### APPENDIX D

Appendix D is primarily a de scription of the field procedures used for the US-EPA Isolation Flux Chambers. The methodol ogy listed on the EPA website was used as closely as possible with so me variations to accommodat e sampling conditions at the specific dairy locations described above. The flux chambers were purchased from Odotech of Toronto, Ontario. The specific methodology is detailed below. Some data in this report (Fig. 6 & 7) is from a mult i-gas analyzer acquired for a project related to this one and used along with the sampling canisters for UCI analysis. The calibration documents for that analyzer alon g with the field sheets to show all of the samples and field data collected at the same time as the UCI canisters are also included in this appendix.

66TESTING METHODOLOGY FOR CSUF S URFACE EMISSION FLUX CHAMBER MEASUREMENTS

Testing will be conducted using Surface Is olation Flux Chamber (flux chamber) to collect emission data. The main technical re ference for flux chamber measurement is a study performed under contract with USEPA that provides a recommended protocol (Measurement of Gaseous Flux rates from L and Surfaces Using an Emission Isolation Flux Chamber, Users Guide, EPA /600/8-86/008, Radian Co rporation, February 1986).

The flux chamber used in this experiment is a clear cylindrical enclosure with a clear spherical top and the fo llowing technical data:

 Material of flux c hamber: Acrylic resin

 Material of tubing: Teflon

 Height of cylinder: 0.24 m

 Height of half sphere: 0.17 m

 Total Height: 0.41 m

 Diameter: 0.495 m

 Ground surface area: 0.19 m 2

 Total volume: 64.5 liters

The testing methodology is given below:

1- Measurements of feed and m anure sources will be made in two (2) separate days. All measurements will be made in the same s equence in all six dairies to provide consistency in environmental conditions betw een dairies, if possibl e (e.g., total mixed ration+0.5 h post placement will be measured firs t, then silage pile, then total mixed ration +6 post placement; or flush lane-pre fl ush will be measured first, then open lot, then flush lane-post flush). At each dairy, fi eld and media blanks will be measured twice at the end of each daily measurement.

2- The sampling plan contains a site map ( aerial photo) with location numbers marked. Each location will represent an average conditi on for the designated areas at the time of measurements.

3- Date, time, test site information, and field and equipment data will be documented on the CSUF SURFACE FLUX MEASUREMEN T DATA FORM. Separate data forms will be used for total mixed ration, silage pile, main feed commodities, and manure sources for regular sampling in the six dairies. Addi tional data will be collected in special sampling for feed sources in two selected dairies. Data forms are shown on pages 8 to13. All the pertinent informati on of the test sites will be collected at the time of measurements (e.g., number and time of feeding, number and time of daily disturbance of silage pile). Information about silage practices and management will be collected separately via survey (see page 14).

674- All measurements will be performed in normal test site conditions without any physical or environmental modifications (e.g., surface of test sites will not be disturbed; total mixed ration and flush lanes will be measured in shade, and normally open lots and silage piles will be measured in sunlight). If possible, the rim of the chamber will be inserted into the measurement surface 2–3 cm to achieve sealing and minimize ambient air intrusion. Additional s ealing will be provided around outside perimeter of the flux chamber if possible.

5- All interior surfaces of flux chambers will be fully washed, rinsed with water, and wiped before the start of measurements. Flux chamber s will be fully dry wiped with a clean paper towel between measurements a nd rinsed with water if necessary.

6- Multiple flux chambers will be used at each test site. INNOVA will collect samples from both flux chambers but only one of the c hambers will be used for other sampling (one UCI canister, one CSUF ca nister, and one TO-17 sample wi ll be collected at each test site). Based on INNOVA real-time data, the flux chamber wit h higher ethanol or methanol emissions will be selected for other sampling in feed sources, and for manure sources, the flux chamber with higher ammonia emissions will be chosen for other sampling.

7- Sweep air flow (ultra zero compressed air) will be initiated immediately after the placement of flux chambers using 1/4-in ch Teflon tubing with stainless still quickdisconnect fitting. The sweep air will be adj usted and constantly maintained to the desired flow rate throughout the measurements using rotameters, metering valves, and pressure regulators. The sweep air flow rate will be set at 10 liters per minute. Sample collection will be performed at steady-state , assumed to be after four residence intervals, or 30 minutes. All 1/4-inch Teflon sample lines will be purged with ultra zero air before sampling.

8- High air temperature inside the flux chamber may cause backpressure and hence could limit diffusional emissions. Ambi ent and flux chamber air and surface temperatures inside and outside the chamber s will be measured immediately when flux chamber is placed and right before samplin g using a hand-held digital thermocouple. Further, air temperature of ambient and flux chamber air will be recorded at all time when flux chamber is placed at the test site using HOBO data logger.

9- Condensation may occur inside the flux chambers in some occasions, which may reduce the concentration of water-soluble volatile organic compounds. The occurrence and degree of condensati on will be noted in the data forms. Further, humidity of ambient and flux chamber air will be m onitored during the course of measurement using HOBO data logger.

10- Rainfall events could alter surface flux rates. Flux chamber measurements will not be taken during and immediately after rainfa ll in open lots and silage piles.

6811- After flux chamber measurements, surf ace samples will be taken from all chamber locations, labeled, and stored in ice chests for laboratory analysis. All feed and manure samples should reach the laboratory within 24 hours.

ANALYSIS SUMMARY The flux chambers will be used for the follo wing procedures at each sampling location:

1. INNOVA unit A

a. Ethanol b. Methanol

c. Trimethylamine d. Isopropanol

e. THC as n-Hexane

2. INNOVA unit B

a. Ammonia b. Nitrous Oxide

c. Carbon Dioxide d. Methane

e. Acetic Acid
INNOVA units will be calib rated at the beginning and at the end of annual measurements or more frequently if needed. Recent (8-9-07) calibration results are shown at the end of this document.

3. UC Irvine - Gas Chromatogr aphy/MS, ECD, FID Detectors

a. Sample Media= 2L canisters b. Number of Com pounds Quantified = 64

4. CSU Fresno – Gas Chromatography/MS (TO-15 and PAMS)

a. Sample Media= 6L summa-type b. Number of Com pounds Quantified: i. TO-15 =62 ii. PAMS (Photochemical Assessm ent Monitoring Stations) = 57

5. EAS Lab Inc. (commercial lab) TO-17 Vo latile Organic Acids from Sorbent Tube

a. Sample Media- Sorbent Tube b. Number of Com pounds Quantified = 5

Documentation of ambient conditions along with material sample documentation and information for sample custody was accomplished through the use of field forms to be filled out for each sampling event. The following forms used for each type of sample. The originals are kept at CS U Fresno as a sample log a nd the data from the forms will be posted to the data webs ite in the near future.

69Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

Main Feed Sources:

1- 4-

2- 5-

3- 6-

Notes:

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dairyland Laboratories Inc. Chamber Dome: %

At TMR+0.5 h:

At TMR+3 h:

At TMR+6 h: Length of Feed Lane (m):

At TMR+6 h: At TMR+3 h: At TMR+0.5 h: Area of Feed Lane (m 2 ):

Notes Measurement Number Time Hours of Feeding:

Number of TMR Push Ups per Day: Site Diagram Chamber Base: %

TMR Information

Number of Feeding per Day:

Hours of TMR Push Ups:

Average Width of Feed Lane (cm): CSUF SURFACE FLUX MEASUREMENT DATA FORM- TOTAL MIXED RATION

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient Flux Chamber Measurements

#

Degree of Condensation:

70Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Type of Measurement: Pile Disturbed Face □ Vertical Undisturbed Face □ Measurement Height: m

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

Notes: Silage Density Measurements:
Height=0.9 m Height=1.8 m
Probe Depth: cm

Probe Diameter: 4.826 4.826 cm

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dairyland Laboratories Inc. CSUF SURFACE FLUX MEASUREMENT DATA FORM- SILAGE PILE

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient #

Silage Information Site Diagram Chamber Base: %

Chamber Dome: %

Type of Silage:

Dates:

Established:

Vertical Undisturbed Exposed Face: Finished (est.):

Disturbance:

Number of Daily Disturbance:

Time of Daily Disturbance: Degree of Condensation: Flux Chamber Measurements

First Disturbed:

Notes Measurement Number Time Date and Time of Last Disturbance:

Area of Exposed Surface (m 2 )

Pile Disturbed Exposed Face:

71Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Open Lot Deep Manure Pack □ Depth= cm

Open Lot Shallow Manure Pack □ Depth= cm

Bedding □ Depth= cm

Flush Lane (Pre-Flush) □ Depth= cm

Flush Lane (Post-Flush) □

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dellavalle Laboratory Chamber Dome: % CSUF SURFACE FLUX MEASUREMENT DATA FORM- MANURE SOURCES

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient Flux Chamber Measurements

Chamber Base: % Degree of Condensation: #

Notes Measurement Number Time Notes Site Diagram

72Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

Main Feed Sources:

1- 4-

2- 5-

3- 6-

Notes:

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dairyland Laboratories Inc.

At TMR+6 h: At TMR+4 h: At TMR+2 h: At TMR+0.5 h: At TMR+1 h:

At TMR+3 h:

At TMR+5 h: At TMR+4 h: At TMR+5 h:

At TMR+6 h: CSUF SURFACE FLUX MEASUREMENT DATA FORM- TOTAL MIXED RATION, SPECIAL SAMPLING (2 DAIRIES)

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient Flux Chamber Measurements

#

Site Diagram Chamber Base: % Degree of Condensation:

Chamber Dome: %

Area of Feed Lane (m 2 ): Hours of TMR Push Ups:

Length of Feed Lane (m): Hours of Feeding:

Number of TMR Push Ups per Day:

At TMR+2 h: At TMR+0.5 h: At TMR+1 h:

At TMR+3 h:

Notes Measurement Number Time Average Width of Feed Lane (cm): TMR Information

Number of Feeding per Day:

73Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Type of Measurement: Pile Disturbed Face □ Vertical Undisturbed Face □ Measurement Height: m

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

Notes: Silage Density Measurements:
Height=0.9 m Height=1.8 m
Probe Depth: cm

Probe Diameter: 4.826 4.826 cm

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dairyland Laboratories Inc. Degree of Condensation: Flux Chamber Measurements

First Disturbed:

Notes Measurement Number Time Date and Time of Last Disturbance:

Area of Exposed Surface (m 2 )

Pile Disturbed Exposed Face: Type of Silage:

Dates:

Established:

Vertical Undisturbed Exposed Face: Finished (est.):

Disturbance:

Number of Daily Disturbance:

Time of Daily Disturbance: Silage Information Site Diagram Chamber Base: %

Chamber Dome: % CSUF SURFACE FLUX MEASUREMENT DATA FORM- SILAGE PILE, SPECIAL SAMPLING (2 DAIRIES)

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient #

74Date: - - 2007 Dairy: Samplers:

Location North □ South □ West □ East □

Feed Source:

Current Activity:

Ambient Conditions: Sun □ P. Sun □ Cloudy □ Rain: Yes □ No □

Notes:

Flux Chamber ID: Prior Chamber Cleaning: Full Wash □ Dry Wipe □ Wet Wipe □ None □

Surface Air Surface Air

10 0 Condensation: Yes □ No □

10 1
10 2
10 3
10 4

10 5

INNOVA □ Event # Sample Line Flushed □

UCI □ Canister # Sample Line Flushed □

CSUF □ Canister #

TO-17 □ Tube #

Photo Taken □ Surface Sample Taken □ Lab Number: Lab: Dairyland Laboratories Inc. Notes: Degree of Condensation: Flux Chamber Measurements

First Disturbed:

Date and Time of Last Disturbance:

Area of Exposed Surface (m 2 )

Pile Disturbed Exposed Face: Finished (est.):

Disturbance:

Number of Daily Disturbance:

Notes Measurement Number Time Vertical Undisturbed Exposed Face: Commodity Information

Time of Daily Disturbance: Type of Commodity:

Dates:

Hauled: Site Diagram Chamber Base: %

Chamber Dome: % CSUF SURFACE FLUX MEASUREMENT DATA FORM- MAIN COMMODITIES, SPECIAL SAMPLING (2 DAIRIES)

Temperature (°C)

Notes Time Sweep Air (L/Min) Residence Number Chamber Ambient #

75INNOVA Calibration Data (8-9-07)

7677 INNOVA Calibration Data (8-9-07)