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Determination of ammonia emission factors for land application of poultry manure 2007

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DETERMINATION OF A M M O N I A EMISSION FACTORS FOR L A N D APPLICATION OF POULTRY M A N U R E b y MARCO WONG B.A.Sc, University of British Columbia, 2005 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRAUDATE STUDIES (Chemical and Biological Engineering) THE UNIVERSITY OF BRITISH COLUMBIA October 2007 Abstract The purpose of this project was to monitor ammonia emissions and develop updated ammonia emission factors for land application of poultry manure under British Columbia conditions. Field experiments were performed at the Agassiz Research Station in 2005 and 2006, which involved four types of poultry manure as the fertilizer materials and four varying heights of the grass canopy. Proceeding manure application, ammonia emission rates were determined using wind tunnels, the emitted ammonia captured using acid traps and analyzed with a flow injection analyzer. For all trials, the highest emissions occurred within the first day, and gradually declined over the next 2-3 weeks. Cumulative ammonia emission in all treatments did not exceed the initial amount of ammonia-nitrogen present in manure. Ammonia emission rates were significantly different among the manure types (p < 0.005). The percent total loss of ammonia with time was positively correlated with manure pH. Ammonia emission rates'were generally higher in both of the spring trials than the fall trial. The ammonia-nitrogen emission rate was found to decrease as the grass height increase. The proposed revised ammonia emission factors of 0.12 and 0.16 kg-NH3-N/initial kg-N for the two major types of poultry - broiler and layer are in line with current emission factors adopted by Environment Canada. However, current and revised emission factors (0.38 versus 0.11 kg-NH3-N/initial kg-N) were substantially different for turkey manure. ii T A B L E O F C O N T E N T S Abstract ii T A B L E OF CONTENTS iii LIST OF TABLES iv LIST OF FIGURES v ACKNOWLEDGEMENTS vi CHAPTER I - Introduction 1 1.1 Introduction 1 1.2 Aim and Scope of the Study 3 1.3 Organization of the Work 4 CHAPTER II - Literature Review 5 2.1 Ammonia Emission Inventory from Agriculture in Europe and USA 5 2.2 Current Canadian Emission Factors 7 2.3 Review of Field Trials for Land Application of Poultry Manure 7 CHAPTER III - Materials and Methods 12 3.1 Spring 2005 Trial 12 3.2 Summer 2005 Trial 14 3.3 Fall 2005 Trial 15 3.4 Spring 2006 Trial 15 CHAPTER IV - Results and Discussion 17 4.1 Spring 2005 Trial 17 4.2 Summer 2005 Trial 19 4.3 Fall 2005 Trial 24 4.4 Spring 2006 Trial 27 4.5 Effects of Temperature and Humidity 30 4.6 Ammonia Emission Factors 32 CHAPTER V - Conclusions and Recommendations 36 5.1 Conclusions 36 5.2 Recommendations 39 REFERENCES 40 Appendix A - Sample Calculations 43 Appendix B - Procedure of Analyses 47 iii LIST O F T A B L E S Table 2.1 Summary of Environment Canada, European and USEPA Emission Factors 8 Table 3.1 Manure Analysis and Application Rates 16 Table 4.1 Change in net weight in orchard grass in relation to the change in height 20 Table 4.2 Daily ammonia emission rates associated with the land application of 24 Table 4.3 Cumulative percent total loss of ammonia over days 1, 2, 3 and 7 28 Table 4.4 Ammonia emitted as a fraction of various forms of initial nitrogen 34 Table 4.5 Comparison of current values and revised values of ammonia emission factors 34 Table 4.6 Manure Analysis and Application Rates 35 iv LIST O F FIGURES Figure 4.1 Ammonia emission rates for four types of poultry manure - spring 2005 trial 18 Figure 4.2 Percent ammonia emission - spring 2005 trial 18 Figure 4.3 Ammonia emission rates for four grass heights - summer 2005 trial „.„ 22 Figure 4.4 Percent ammonia emission - summer 2005 trial 22 Figure 4.5 Average wind speed profiles as a function of height from soil surface (July 13-14, 2005) 23 Figure 4.6 Average wind speed profiles as a function of height from soil surface (July 20, 2005) 23 Figure 4.7 Ammonia emission rates for the various types of poultry manure - fall 2005 trial 26 Figure 4.8 Percent ammonia emission - fall 2005 trial 26 Figure 4.9 Ammonia emission rates for the various types of poultry manure - spring 2006 trial 29 Figure 4.10 Percent ammonia emission - spring 2006 trial 29 Figure 4.11 Temperature measurements for the spring and fall trials 31 Figure 4.12 Relative humidity measurements for the spring and fall trials 31 ACKNOWLEDGEMENTS I would like to express my deep appreciation to my thesis committee, Dr. Anthony Lau, Dr. Sue Baldwin, and Dr. Lim, for their guidance, review, suggestions, kindness, valuable time, criticisms, and comments throughout my graduate study. I am most grateful to Professor Dr. Anthony Lau for his encouragement from the very beginning of the study, and for guiding me in the research and analysis. Funding by Environment Canada under the National Agri-Environmental Standards Initiative (NAESI) program towards this project is gratefully acknowledged. Special thanks are due to Dr. Shabtai Bittman and his team (Derek Hunt, Frederic Bounaix, Anthony Friesen, Kate Swift and Alison Ma) at the Agriculture and Agri-Food Canada Agassiz Research Station for their advice and assistance in setting up the field trials, collecting data and performing the chemical analysis. vi CHAPTER I - Introduction 1.1 Introduction Ammonia (NH3) emissions, being next to sulfur dioxide (SO2) and nitrogen oxides (NOx), are important contributors to the eutrophication and acidification of natural ecosystems. Its contribution to the formation of fine particulate matter and smog has also received increasing attention in recent years (Lefebvre et al. 2005). Concern about the role of ammonia as a precursor to environmental and health impacts led Environment Canada to declare ammonia as a toxic substance under the Canadian Environmental Protection Act (CEPA) in 2003. Ammonia is included in the international Gothenburg Protocol, which requires that all signatory nations quantify and reduce their emissions in relation to 1990 levels. Ammonia emissions from farm operations have been identified by the National Agri- Environmental Health Analysis and Reporting Program (NAHARP) as one of the quantitative indicators of agricultural environmental performance in Canada. Based on current estimates, about 6% of all Canadian emissions can be attributed to land application of poultry manure. Poultry production in British Columbia constitutes some 15% of the total production in Canada, and the Fraser Valley of B.C. generates large quantities (approximately 280,000 tonnes) of poultry manure each year. The ammonia found in poultry manure partially results from the uric acid produced as an end- product of nitrogen catabolic process; the uric acid decomposes into urea and finally ammonia. The ammonia enters the nitrogen cycle in its ionic form, ammonium NH4 + . It is oxygenated by nitrifying bacteria into nitrite in the soil, and then converted to nitrate in a process called nitrification. Ammonium ions readily bind to soils due to its positive charge. Nitrate and nitrite ions, due to their negative electric charge, bind less readily since there are less positively charged ion-exchange sites in the soil than negative sites. Leaching of nitrate and nitrite into groundwater can occur from precipitation or irrigation because of their solubility. Nitrites can be reduced to nitrogen gas through denitrification by anaerobic bacteria. 1 While land application of poultry manure can provide essential plant nutrients for crop production, improper manure management can lead to ammonia volatilization from the litter, and it can be detrimental to the environment. The deposition of ammonia in the natural ecosystem leads to eutrophication of lakes and rivers, and the nitrification of ammonia into nitrate, causing contamination of groundwater such as a regional aquifer. In the atmosphere, ammonia decomposition into nitrites and nitrates contributes to acid rain and the formation of ammonium- based particulate matter. Particles including ammonium nitrate and ammonium sulfate cause health problems such as chronic heart disease and lung cancer, and also account for 75% of the visibility impairments in the Lower Fraser Valley. As an extension to the United Nations' 1979 Geneva Convention on long range trans-boundary air pollution, the International Gothenburg Protocol aims for the abatement of acidification, eutrophication and ground-level ozone. Signed on November 30 , 1999 by many European countries, one Asian country (Armenia), the USA and Canada, all signatory nations are required to reduce sulfur, NO x , V O C and ammonia emission compared to 1990 levels. The principle objective of this project is to monitor the seasonal variations of ammonia emissions from land application of poultry manure, in order to derive updated emission factors for the BC as well as ammonia indicator and inventory. These revised emission factors, which are defined as either "an emission percentage based on an initial mass present in the manure, expressed as mass of ammonia emitted per initial mass of ammonia nitrogen", or "an emission rate of ammonia per bird per year", will be compared to the emission factors currently adopted by Environment Canada (EC), and used as inputs to model atmospheric NH3 transport. The aim is to forecast how it reacts in the atmosphere to form aerial particles. The final results will be used to re-tool agricultural management practices and set goals for emission reductions. This paper presents the findings from literature survey on ammonia emissions from arable land applied poultry manure, and ammonia emission results obtained from field experiments conducted during the spring, summer and fall periods of 2005, as well as spring 2006. 2 1.2 Aim and Scope of the Study Earlier studies on ammonia emissions were largely concentrated on dairy and swine manure. Some research studies have been done on the ammonia emission from land application of poultry manure, but involve other variables including but not limited to manure incorporation, precipitation, and fertilizer pellets usage; very little has been done on turkey-manure. Also, the grass canopy height on the effects of ammonia volatilization had never been addressed. Uric acid contents of various types of poultry manure have been measured in other studies; however, its effects on the ammonia release rate upon manure spreading have not been investigated. The emission factors currently adopted by Environment Canada contain certain assumptions and are not region-specific, and therefore, the development of an emission factor inventory in British Columbia would more accurately represent the ammonia emissions from land spreading of poultry manure in the province. A more controlled experimental atmosphere is desirable. The goal of this thesis research is to observe the seasonal variation effects on the volatilization of ammonia from the land application of layer, broiler, breeder, and turkey manure. Specific objectives include: 1. To determine the ammonia emission factors in relation to the seasonal variation and poultry manure type; 2. To determine the relationship between ammonia volatilization and the height of grass on which manure is applied; and 3. To determine the uric acid content in manure and its contribution to the release rate of ammonia. 3 1.3 Organization of the Work The thesis is contains 6 chapters. Chapter 1 is an introduction to the problems associated with ammonia emissions from the land application of poultry manure. The aim and scope of this study as well as the organization of the work are also presented in this chapter. Chapter 2 gives and in- depth literature review of previous ammonia inventory studies done in Europe-and United States, the current Canadian inventory, and preceding trials on the application of poultry manure. The emphasis of Chapter 3 is on the methodology utilized in the experiments. Chapter 4 discusses the results from the four trials performed, the effects of atmospheric conditions, and the ammonia emission factors obtained. Finally, the conclusions are presented in Chapter 5, summarizing the findings and recommendations. 4 CHAPTER II - Literature Review 2.1 Ammonia Emission Inventory from Agriculture in Europe and USA Ammonia emission originates primarily from agricultural activities. Livestock production in Europe is the predominant source (70 to 90 percent of total emissions) folldwed'by application of mineral N-fertilizers (up to 20 percent of total). The most recent inventories rely on country or region specific data on N-excretion and management practices. They distinguish between different manure systems to assess losses of nitrogen at the various stages of manure handling. This method is often referred to as "N-flow" or "process-based model" (Misslebrook et. al. 2000). It relies on the assessment of available nitrogen and NH3-nitrogen at each considered stage (housing, storage, application) and its potential loss as ammonia. Recently, this method has gained wider acceptance, and has been used for the national ammonia emission inventories of the UK, Denmark, Germany, Netherlands, Switzerland and Norway (Kuczynski et. al. 2005). After spreading of manure, the following factors play an important role in determining N-losses: meteorological conditions including temperature, humidity, turbulence, precipitation, soil properties including pH, calcium content, water content, manure properties such as pH, viscosity, dry matter content, the application rate, and the way manure is applied. The diet of poultry, type of poultry, the bedding as well as other additives to the manure litter dictates manure pH. The storage period allows for decomposition of the manure, which would also change the pH of the manure. The minimum information necessary to arrive at region-specific emission factors for each animal type includes typical N excretion rates, the manure application method, N- volatilization rates for different application practices. If emission factors during the manure application stage are based on N-excretion during the housing stage, it is necessary to know the N-volatilization rates during the housing stage, the manure storage stage and the manure application stage. National inventories and projections for ammonia emissions in Austria, Germany and Ireland are compiled by using methodologies agreed upon by the Convention on Long Range Transboundary Air Pollution (CLRTAP) as set out in the Joint EMEP/CORTNAIR Atmospheric Emission 5 Inventory Guidebook 2003. Emission factors of poultry manure from many European countries as well as the USEPA and Canada are shown in Table 2.1 below. This guidebook outlines a detailed method and a simple method for calculating these emission factors. The detailed methodology requires input data of animal numbers, nitrogen excretion, and manure management systems. Ammonia emissions from dairy cows, other cattle, fattening pigs and sows are estimated with the detailed methodology. In contrast, the simple methodology- uses an average emission factor per animal for each livestock category and multiplies this factor by the number of animals counted in the annual agricultural census. Emissions from laying hens, broilers, other poultry, sheep, horses, and other farm animals are estimated using the simple method. There are problems with the simple method since there is no actual measurement data for most ammonia emitting activities (housing and storage). As well, uncertainties in emission values arise from oversimplified representations and related assumptions to quantify emissions in broad source categories. ECETOC (European Centre for Ecotoxicology and Toxicology of Chemicals) assigns emission factors as proportion of total N applied for each livestock type; for instance, 28.5% of total N was determined for cattle manure, 5.35% for pig manure, 37.6% for laying hens and 7.2% for broilers. However, EMEP/CORINAIR gives 20% of total N for manure from all livestock types. It is apparent that updated information on manure storage and manure management practices is necessary for improvements in the method currently used in estimating the emission factors. In more recent documents (Kuczynski et al., 2005; USEPA, 2005), ammonia emission factors are given either in units of [percent initial total nitrogen or TN, %TN], or [kg NH3/animal/year]. USEPA suggested values of 42% TN for wet layer manure versus 7% T N for dry layer manure, whereas turkey manure is assumed to have the same value of 25% TN as broiler manure. By comparison, data from Norway indicated a range of 4% TN (spring) to 10% T N (autumn) for dry poultry manure. Ammonia emission factors, expressed in units of [kg NHa/animal/year], are also available for total emissions from the combined activities of housing, storage and land application (for instance, in Austria, Czech Republic, Finland, Russia and USA). However, data for land application of poultry manure alone are very limited. USEPA adopted (2005) a single average value of 0.24 kg MVanimal/year for all types of poultry. 6 2.2 Current Canadian Emission Factors For land application of poultry manure, the current Canadian emission factors are classified as "uncontrolled emission" and "controlled emission", and according to the types of poultry manure: pullets (< 19 weeks), laying hens (> 19 weeks), laying hens in hatchery supply flocks, broilers (and roasters and Cornish), turkeys and other poultry (including ducks andj*eese) (Environment Canada 2005). Magnitudes of "uncontrolled emission factors" are based on the assumption that 50% of initial available N is volatilized as NH3 -N , and reported as the amount of NH3 volatilized as [% TN]. In the category of emission factors associated with "controlled emission", expressed in units of [kg NH3/animal/year], values currently adopted by Environment Canada are compatible with the European data for the various types of poultry manure. A summary and comparison of Canadian, European and US emission factors may be seen in Table 2.1. 2.3 Review of Field Trials for Land Application of Poultry Manure Ammonia (NH3) emission inventories are required for modeling atmospheric NH3 transport and estimating downwind deposition. The derivation of the UK-based emission factors used in the calculation of that emission for a range of livestock classes, farm practices and fertilizer applications to agricultural land was described in (Misselbrook et. al. 2000). An emission factor of 45% U A N (uric and NH3-N) content of the poultry manure was estimated from the results of field experiments. The average U A N content varies according to poultry type. A research study (Battye et. al. 2003) used poultry excretal output, among other livestock classes, for estimating the quantity of manure for land application. The researchers concluded that the slow conversion of uric acid to urea could lengthen the ammonia emission period. Ammonia emission factors from several European nations, USEPA and Environment Canada are presented in Table 2.1. 7 Table 2.1 Summary of Environment Canada, European and USEPA Emission Factors Emission factor, kg NH3/animal/year Based on total emissions (housing, storage, land application etc) Layer Broiler Turkey Austria 0.22 0.17 0.54 Data not available for land application Czech Republic 0.27 0.21 0.73 Russia 0.37 0.28 0.92 Finland 0.34 0.055 n/a Russia minus Austria 0.15 0.11 0.38 Environment Canada 0.15 0.12 0.38 USEPA 0.24 (composite value for all types of poultry) 2002 data (most recent) Emission factor, percent of T N Based on emissions during land application only Holland 19.5% 18.4% Assuming TN in manure = 45% * TN in diet ECETOC 37.6% 7.2% USEPA 42% (wet); 7% (dry) 25% 25% Assuming turkey same as broiler's EMEP/CORINAIR 20% For all livestock types Norway 4% (spring) to 10% (autumn) For dry manure *Huijsmans et al 2003 3.3 to 24% (highest in summer) *Rodhe and Karlsson 2002 13.5% (broiler) 8 It is common practice amongst poultry fanners of the lower mainland to store manure in house or in storage throughout the year until a large quantity has been accumulated. Because farmers have to manage the large amounts of manure, or have fields that require large amounts of manure consistently, perennial grass such as orchard grass is ideal for its rate and amount of N uptake (Kaffka et. al. 1996). Also the variation in climate has minimal effect on fhe_overall orchard grass growth and N uptake, meaning farmers can estimate the N uptake even with a range of possible conditions and manage nutrients to reduce undesirable N losses. Nitrogen uptake by orchard grass continues throughout the growing season and not just the first growth cycle, allowing for multiple experiments with longer durations. A diurnal rhythm of emission was evident with higher emission during the day and lower emission at night (Wulf et. al. 2002); this can be attributed to temperature effects on NH3 solubility and the equilibrium concentration of NH3 and NH4+ according to Henry's law. There are guidelines on the poultry manure application rates for different vegetable crops, grass and cereals (British Columbia Ministry of Agriculture, Fisheries and Food. 1997). The application rates are usually based on nitrogen (typical nitrogen uptake by the plants in kg/ha), if excess phosphorus and potassium do not cause environmental concerns. Because this study is focused on ammonia emission from land applied manure, the application rate follows the nitrogen-based application guidelines for perennial crops such as orchard grass. It depends on the moisture content and nitrogen content of manure; greater application rates are required if moisture content is higher and nitrogen content is lower. A series of experiments were conducted using small wind tunnels to assess the influence of a range of environmental, manure and management variables on ammonia emissions following application of different manure types to grassland and arable land (both to stubble and growing cereal crops), in keeping with common practice in the U K (Goebes et. al. 2003). Wind speeds through the tunnel canopies were controlled at 1 m s~'. The concentration of N H 3 - N in both the air entering and leaving each tunnel was determined by drawing a sub-sample of air (at 3-4 1 min - 1) through absorption flasks containing phosphoric acid. Measurements of NH3 emission continued for 12 d following solid manure applications. In addition to NH3 emissions, measurements were also made of manure dry matter (DM) content, pH, total N content, total 9 NH3-N (TAN) content and uric acid N content, plus soil moisture content and soil pH (top 10 cm), crop height (and growth stage for cereals), wind speed (at a height of 25 cm), air and soil temperatures (at 5 cm height and 5 cm depth, respectively) for each experiment. Differences in temperature were achieved by applying manure at different times of year. For solid manures, rainfall was identified as the parameter with most influence on ammonia emissions by leaching into the soil matrix thence the local aquifer. — A multi-season study was conducted to quantify NH3 volatilization rates from surface-applied poultry litter under no-till and plowed conservation tillage managements (Huijsmans et. al. 2003). Litter was applied to supply 90 to 140 kg N ha - 1 . Poultry litter was applied immediately after planting and before seed germination, with the standing stubble from the previous crop being 10 to 15 cm tall. Micrometeorological data and atmospheric NH3 concentrations were determined 24 to 48 h before litter application and for 7 to 8 d following applications. Results showed that ammonia volatilization was rapid immediately after litter application and stopped in about a week. Total losses of NH3 from surface-applied poultry litter ranged from 3.3 to 24% of the total N applied with the largest losses under summer (hot, dry, windy) conditions. Losses of 22 to 24% would be large enough to potentially decrease crop yields when poultry litter is used as the sole source of N fertilizer and applications are based on the N content of the litter. In addition losses of this magnitude have the potential to affect nearby natural ecosystems. Precipitation (rainfall) of 17 mm within 48 h of application greatly inhibited volatilization rates, probably by transporting litter N into the soil matrix, although 36 to 64% of the ammonia in the poultry litter was volatilized before precipitation. Application of poultry to conservation-tilled cropland immediately before rainfall events would reduce N losses to the atmosphere but could also increase NO3 leaching and runoff to streams and rivers. A spreading experiment was conducted at Ultuna, 5 km south of Uppsala, Sweden. After storage, broiler manure and commercial fertilizer pellets (a mixture of broiler manure, harvest residues and stone meal) were spread to arable land at a rate of 110 kg [total-N] ha - 1 (Misselbrook et. al. 2005), which corresponds to a rate of 4.4 t broiler manure per hectare and 2.7 t pellets per hectare. The broiler manure was applied with a spreader JF, type ST70-H, modified as a two-step spreader. The soil had a texture classified as clay and 2-3% organic matter. The treatments were arranged as a randomized block design with three replicates. Ammonia emissions were measured 10 from plots fertilized with broiler manure and pellets, respectively, with and without harrowing 4 h after spreading. For plots fertilized with broiler manure with no incorporation of the manure into the soil, the NH3 emissions were measured on five occasions over a period of 5 days and for plots fertilized by broiler manure and harrowed 4 h after spreading on three occasions during 2 days. The pellets were also applied plots, with and without incorporation. Totally, 13.5% of the nitrogen in the broiler manure was lost as ammonia after spreading wifhouHncorporation of the manure and 7.5% from plots with incorporation. After incorporation no ammonia emission occurred. No emissions occurred from plots fertilized with pellets. Incorporation after spreading of broiler manure was found to be an effective way to reduce ammonia emissions. The incorporation should be carried out as soon as possible after spreading, or at least not more than 4 h after spreading, to limit the ammonia losses to about half of the potential amount. Based on a project specific to broiler litter and layer manure (Anon 2003), where manure was applied to land at a target rate of 250 kg N/ha (though actual rates varied from 120 to 470 kg N/ha), research findings indicated there were no differences in emissions between any of the broiler litter treatments following land spreading, with total ammonia losses equivalent to 46- 92% (average 63%) of the U A N applied over the 28 day measurement periods. Likewise, there were no differences in emissions following land spreading between the various layer manure removal methods or between layer manures from the different commercial unit houses. Total ammonia losses were equivalent to 67-118% of the U A N applied over the same period; however, no explanation was given as to how losses could possibly exceed 100%). 11 CHAPTER III - Materials and Methods 3.1 Spring 2005 Trial Field tests were performed at the Agassiz Research Station of the Pacific Agricultural Research Center (PARC) in May-June 2005 using four different types of poultry manure (breeder, broiler, layer, and turkey) as the fertilizer materials. The manure was collected fronveommercial poultry farms within the Fraser Valley of B.C. for this trial, as well as for the summer 2005, fall 2005 and spring 2006 trials. The various types of manure were either fresh from housing, had been stored in-barn, or as a covered-pile outdoor. After manure application, wind tunnel canopies were positioned over each plot with air drawn through at a constant and controlled rate. Sixteen framed wind tunnels were installed for the experiments, with the frames set 50 mm in the ground. Polycarbonate covers were secured on the frames immediately after manure application. Each tunnel has the general height of is 450 mm and a width of 500 mm. A rotary anemometer was mounted inside the blower unit of each tunnel, with an orientation perpendicular to airflow. Airflow rates from the anemometers inside the tunnels were transmitted to a multiplexer and a CR10X data-logger via a signal transmitter box. Four of the 16 anemometers contained temperature probes which monitored ambient temperature within the tunnel. This data was also transmitted to the CR10X data-logger. Data were downloaded periodically from the data-logger onto a laptop computer. Air sample inlet for the tunnel was located above the blower. Acid traps were set up using graduating cylinders containing 100 ml of 0.01 M phosphoric acid to capture ammonia from the sample. With suction from a pump, a sub-sample of tunnel air (at 2-3 L/min) was bubbled through the acid solution via a Tygon tube placed at the inlet of each tunnel and the inlet of the blower. Each unit was connected to an Erlenmeyer flask to capture condensate. Flow restrictors were used to reduce the load on the pump. The volume of air sampled was measured using flow meters. All equipments were placed inside weatherproof wooden boxes. The wind tunnel method and ammonia capture technique used in this study is similar to that used by Misselbrook et al. [1]. On the first day when the rate of NH3 volatilization was anticipated to be highest, the acid traps were changed and replenished at time intervals of 1 h, 2 h, and 5 h following manure application. 12 Thereafter, 1-2 shift changes occurred in the morning and mid-afternoon for 8 days, and once a day after that until Day 21. A total of 32 liquid samples (2 bubblers per tunnel) obtained from each acid change shift were stored in a cooler at 5°C. Samples were prepared for analysis by filling the liquid levels to 120 ml if the bottles should contain fewer amounts due to field evaporation of the acid solution as a result of heat from the environment and the pumps inside the boxes. Once prepared, they were analyzed using a flow injection analyzer (FLA). The amount of N H 3 volatilized during each interval was calculated from the amount of NH3 trapped and the airflow data. A randomized complete block design was adopted for the experiment, with 4 treatments for the various types of poultry manure having 4 replicates for each treatment. Preceding application, manure samples were analyzed for moisture content, ammonia-nitrogen, and total nitrogen contents; pH values were also measured for the spring and fall 2005 manure samples. Material balance on N was not done for this study because ammonia emission was the main concern; hence, leachate or runoff was not measured. The total nitrogen content of the manure is important for the determination of its fertilizer value. Proximate analyses included manure pH and moisture content and elemental analyses consisted of total nitrogen (TN) and total ammoniacal nitrogen (TAN) contents. The C:N ratio was not measured because the manure was used directly as fertilizer, rather than for composting purposes. Other elemental analyses were not analyzed because they would have little or no effects on ammonia volatilization. Other proximate analyses such as ash or electrical conductivity were not measured because they are not important information for land application of manure. Based on these analyses, manure was surface-applied by hand to the plots (0.5 x 2 m). In the spring and summer trials, the quantity of manure applied as shown in Table 3.1 was based on ammonia-nitrogen, which is equivalent to 100 kg NH4-N/ha or 470 kg N/ha, respectively. In the fall trial, the application rate was based on total-N. Measurements of NH3 emission continued for 21 days following manure application. Using the data associated with the sub-sample of tunnel airflow during each shift change, and assuming that ammonia capture rate is equal to the ammonia emission rate, the latter was computed from the trapped ammonia concentration values. The ammonia emission rate from the 13 entire plot was then computed using the ratio of actual airflow rate (from the rotary anemometer readings) to the sub-sample airflow rate. Thus, E = (C 0 - CO V R Eqn. 1 Where E is ammonia emission rate based on sub-sample tunnel air, [mg per interval]; C0 is -<K. concentration of ammonia at blower intake; C, is concentration of ammonia at tunnel intake; V is volume of acid trap solution; R is the ratio of actual airflow rate to the sub-sample airflow rate =v A/Q; v is rotary anemometer speed anemometer wind speed; A is tunnel cross sectional area, and Q is sub-sample tunnel flow rate tunnel flow rate These calculations were performed for all shifts of all tunnels. 3.2 Summer 2005 Trial The trial was performed in July 2005 using broiler manure as the fertilizer material. The experimental setup was essentially the same as that of the spring trial except the treatments comprised of 4 heights of orchard grass (low 25 mm, medium-low 75 mm, medium-high 175 mm, and high 275 mm) with 4 replicates for each treatment. Manure was surface applied to the plots (0.5 x 2 m) by hand at a rate of 2.79 kg per tunnel or per m 2, the same as that used for the spring trial Prior to spreading broiler manure onto the plot, four different grass heights were cut to study the effects of canopy height on ammonia emission. A lawn mower was used to cut the shortest two heights, which came out to average grass heights of 25 mm and 75 mm, respectively. The third height was trimmed using shears with a piece of wood used as a height reference; the average height came out to 175 mm. Uncut grass was used as the final and tallest canopy with an average of 275 mm. The effect of turbulence was observed from the four different heights of grass. A hot wire anemometer was inserted through three holes drilled into the polycarbonate canopy cover of each wind tunnel to measure the varying wind profiles. A total of 15 points were collected for each hole, where each point is an average of 5 wind velocity reading from the hot wire anemometer. 14 The average values between replicates were used to demonstrate the average wind profile for each treatment. 3.3 Fall 2005 Trial Field tests were performed at in November-December 2005 using poultry manure as the fertilizer materials. A randomized complete block design was used for the experiment, jwifh 4 treatments for the various types of poultry manure and 4 replicates for each treatment. Manure was surface applied to the plots (0.5 * 2 m) by hand after weighing out specific amounts. The initial amounts of manure applied are also reported in Table 3.1, and the application rate is based on 150 kg N/ha. Measurements of NH3 emission continued for 21 d following manure applications. After the experiment, Tygon lines running from the acid bubbler to the overflow cylinder and the overflow cylinder itself were washed with acid. This acid washing fluid sample was collected to measure any residual ammonia that may have been trapped in the lines or in the overflow as condensate. As well, manure scrapings were collected from each treatment plot to be analyzed again for ammonia-nitrogen content. 3.4 Spring 2006 Trial Field tests were performed at Agassiz Research Station of PARC in April 2006 using poultry manure as the fertilizer materials. A randomized complete block design was used for the experiment, with 4 treatments for the various types of poultry manure and 4 replicates for each treatment. Manure was surface applied to the plots (0.5 x 2 m) by hand after weighing out specific amounts. The initial amounts of manure applied are reported in Table 3.1, and the application rate is based on 150 kg N/ha, which is same as the previous trial in the fall. Like the spring 2005 trial, both the moisture content and ammonia nitrogen content of layer manure were greater than those of the other three types of manure. Based on the daily ammonia emission rates, ammonia emission was calculated as a fraction of the initial amount of ammonium-N present in applied manure. These values were then multiplied by the ratio of "ammonium nitrogen-to-total nitrogen" (NH4:TN), and the ratio of "ammonium nitrogen-to-uric acid and ammonium nitrogen" (NH4:UAN), in turn, to obtain seasonal emission factors. Statistical analysis of the ammonia emission results over 2 days, 7 days and the end of 15 each trial period (2-3 weeks) was performed via the analysis of variance (ANOVA), which is a collection of statistical models. If the overall "p value" from the A N O V A is small, for example p < 0.005, it means it is unlikely the differences observed are due to random sampling, and that there is significant differences between treatments. Table 3.1 Manure Analysis and Application Rates-- Type of manure Application rate, kg/m2 Moisture content, % w.b. Total nitrogen, % d.b. Ammonia- N, % d.b. NH3:TN pH Spring 2005 Manure Types Trial breeder 2.08 33.3 2.98 0.72 0.24 8.4 broiler 2.79 36.7 2.67 0.57 0.21 8.5 layer 1.26 79.5 6.26 3.88 0.62 6.5 turkey 0.74 41.6 7.35 2.33 0.32 8.4 Summer 2005 Grass Heights Trial broiler 2.79 36.7 2.67 0.57 0.21 8.1 Fall 2005 Manure Types Trial breeder 0.56 23.0 2.89 1.22 0.42 8.8 broiler 0.68 32.1 3.06 0.52 0.17 8.9 layer 0.30 13.4 5.90 0.82 0.14 7.9 turkey 0.30 29.0 7.53 1.84 0.24 5.9 Spring 2006 Manure Types Trial breeder 0.52 31.7 4.26 1.20 0.28 7.3 broiler 0.41 22.1 4.73 0.90 0.19 7.5 layer 0.71 53.7 4.55 2.53 0.56 7.3 turkey 0.36 29.6 5.95 1.26 0.21 6.7 w.b.: wet basis d.b.: dry basis 16 CHAPTER IV - Results and Discussion 4.1 Spring 2005 Trial From the data associated with the sub-sample of tunnel airflow during each shift change, and assuming the ammonia capture rate is equal to ammonia emission rate, the hourly and hence daily ammonia emission rates were computed from the trapped ammonia concentration values. Results are shown in Figure 4.1 with the standard error bars that represent a 95% confidence interval. The manure exhibited emission results as expected, with the highest emissions at 1400, 2600, 800 and 1200 mg/d for breeder, broiler, layer and turkey manure, respectively, occurring within the first day then gradually decreasing in the 16-day period of measurements proceeding manure application, although zero emission was not achieved. Based on these results, the total amount of ammonia emitted over the monitored period was estimated and expressed in terms of the initial ammonia-nitrogen content of the manure, as depicted in Figure 4.2. Cumulative ammonia emission in all treatments did not exceed the initial amount of ammonia-nitrogen present in manure. Total ammonia emissions were significantly different between the manure types (p < 0.005). 17 Ammonia emission following land application of various types of poultry manure 3000 1 E 2500 2000 1500 1000 500 • 1 I I - 1 — u t[ i wtfU IBL f i l l —n 4 5 6 Days After Application I B reede r • Bro i le r • Layer • Turkey Figure 4.1 Ammonia emission rates for four types of poultry manure - spring 2005 trial Fraction of initial ammonia-N emitted over a period of 2, 7 and 16 days 1 w 60.0 50.0 40.0 30.0 20.0 10.0 0.0 Breeder Broiler Layer Turkey Treatment Figure 4.2 Percent ammonia emission - spring 2005 trial 18 4.2 Summer 2005 Trial The profiles of ammonia emissions over 14 days are shown in Figure 4.3 for the four orchard grass heights, with standard error bars (95% confidence) indicating the variation due to the replicates. The general ammonia emission trend was similar for all treatments. The NH3 volatilization rate from applied manure was rapid immediately (day 1) after manure application and declined with time, as expected. Ammonia emissions were consistently-higher for the low (25 mm) and medium low (75 mm) grass heights, whereas the lowest emission was associated with the high (275 mm) grass. The wind speed collectively with taller grass canopy was able to take up more NH3-nitrogen form the manure. Nevertheless, A N O V A results showed the total NH3 emissions over the 2-week period were not significantly different (p > 0.10) between the grass heights. As shown in Figure 4.4, losses of ammonia during this period amounted to 65%, 60%, 56% and 43% of the initial ammonia-N for the orchard grass heights of 25 mm low grass, 100 mm medium-low grass, 175 mm medium-high grass and 275 mm high grass, respectively. When compared to the initial amount of total N in the broiler manure, such losses ranged from 9.1 to 13.9%. This is in good agreement with results obtained by Rodhe and Karlsson (2002), (13.5% of the nitrogen in the broiler manure was lost as ammonia over the first 5-day period), for plots fertilized with broiler manure with no incorporation. It is also in the same order of magnitude (3.3 to 24%) as reported by Sharpe et al. (2004), who considered losses of 22 to 24% to be large enough to potentially decrease crop yields when poultry litter is used as the sole source of N fertilizer and applications are based on the N content of the litter. According to Fulhage and Pfost (1994), until poultry manure is incorporated into the soil, its ammonia-N losses generally ranged from 20% within two days of application, to 80% after 7 days of application; in other words, only 20% of initially applied ammonia-N is available for crops if it took more than 7 days till incorporation. There are two hypotheses that could explain the lower ammonia emissions from taller grass in comparison to higher emissions from shorter grass: either the taller grass has the ability to uptake more nitrogen from the manure, or the taller grass resulted in less turbulence at the soil-manure interface. The height of the grass is directly related to the depth of the root system; because the 19 grass initially for all treatments was the same height before trimming, and manure application was immediately following grass trimming, the root system should be the same at the start of the trial. In general, taller grass is able to uptake a larger amount of nitrogen and has more surface area to harvest light energy to use for growing roots for nitrogen uptake, and for growth. Therefore, the uptake of nitrogen from the manure to the grass is greater for taller grass. In addition, the shorter grass may have taken less nitrogen as a result of the amount trimmed from the grass. A general rule for lawn maintenance is to cut no more than a third of the grass in order to not stress the plant. As a result of the extensive trimming, the plant loses its photosynfhetic ability causing root death. The change in nitrogen of the orchard grass and the change in grass height can be seen in Table 4.1. A positive correlation can be seen between the initial grass height and the ratio between the changes in the net weight to the changes in grass height. Table 4.1 Change in net weight in orchard grass in relation to the change in height Trt ANW,g St Dev AGH, inches ANW /AGH LO 0.97 0.23 12.1 0.080 ML 1.42 0.16 13.0 0.109 MH 1.65 0.18 10.1 0.163 HI 1.37 0.19 7.5 0.183 It is also very likely the taller grass canopy created a boundary layer which reduced the air flow below the canopy, increasing flow through the upper portion of the wind tunnel. With taller grass, the resistance of air flowing through the grass increases due to a denser canopy; with the air flowing through each wind tunnel conserved, this forces air to flow above the grass canopy. The turbulence decreases at the manure-air interface as a result of lower air flow rate, consequently reducing the flux of ammonia between the air and manure. Higher air velocities at the ground-air interface could have promoted more air mixing within this zone, thus increasing the diffusion of ammonia lowering the NH3 concentration in the air above the manure, and eventually stimulating further N H 3 volatilization. This relationship between wind speed and ammonia volatilization explains why the most emissions were seen in the low grass (higher wind speeds). In this aspect, Huijsmans et al. (2003) had observed that wind speed exerted a substantial effect on the volatilization rate, only when manure was surface applied or 20 surface incorporated. It can be seen in Figure 4.3 that there is very little difference in ammonia emission between the medium low and low grass throughout the trial. On the first day, it is very evident the highest grass resulted in the lowest emissions, followed by the medium high grass. Moreover, the high grass emitted over 1000 mg less than medium low and low grass on the first day immediately following application, and remained the treatment with the lowest emission for the first 7 days. While the growth of grass is greatest for the lower grass-heights, the emission rate remains the highest. Therefore, it is more likely that the differences between the ammonia emission rate is related to the wind speeds at and near the soil-manure interface as oppose to the uptake of ammonia by the grass. Examination of the rotary anemometer readings indicated that the measured data were relatively constant for all tunnels during the field test period; however, they were different among the treatments, for instance, the average reading was 11.78±0.31 m/s for the medium low grass height, whereas it was 14.23±0.06 m/s for the low grass height. The wind speed profiles derived from the hot wire anemometer measurements on two occasions are shown in Figures 4.5 and 4.6. Air velocity is seen to increase with height from the soil surface; moreover, as grass height increases, the difference in air velocity between treatments increases in the zone 20-40 cm above the soil surface, this relationship being most pronounced for the high grass. This relationship is a result of the wind speed being conserved within the tunnel; that is, lower wind speeds within the grass canopy are associated with relatively higher wind speeds within the upper region of the tunnel. 21 Ammonia emission following land application of broiler manure in plots with varying grass height 5000 E, 4000 c o "55 .S2 3000 E 3 to '§ 2000 E E Z, 1000 •« Q • Medium Low 75mm • Medium High 175mm • High 275mm • Low 25mm rn/i ^ 3 5 7 10 Days after land application 14 Figure 4.3 Ammonia emission rates for four grass heights - summer 2005 trial Fraction of initial ammonia-N emitted over a period of 2, 7 and 14 days 80 70 5? SO 40 30 2 0 10 • 14 day average % N H 3 emiss ion El 7 day average % N H 3 emiss ion • 2 day average % N H 3 emiss ion grass height 275 mm grass height 176 mm grass height 75 mm Treatment Figure 4.4 Percent ammonia emission - summer 2005 trial grass height 25 mm 22 Hot Wire Anemometer Wind Speed Relation to Height - July13-14, 2005 1.800 -i — — — — • 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 Height From Soil Surface (cm) | • LP • ML A MH o HI Poly. (LP) Poly. (ML) Poly. (MH) - - - Poly. (HI) | Figure 4.5 Average wind speed profiles as a function of height from soil surface (July 13-14,2005) Hot Wire Anemometer Wind Speed Relation to Height - July 20, 2005 0.00 ' o 5.00 10.00 15.00 20.00 25.00 Height From Soil Surface (cm) 30.00 35.00 40.00 | • LP a ML A MH o HI - - - Poly. (HI) - - - Poly. (MH) Poly. (ML) Poly. (LP) | Figure 4.6 Average wind speed profiles as a function of height from soil surface (July 20,2005) 23 4.3 Fall 2005 Trial As shown in Table 3.1, the initial layer manure ammonia content was significantly less for the fall 2005 trial (0.82%) than that for the spring 2005 trial (3.88%). The manure from the spring trial was observed to be very wet and thus trapped more ammonia, which could explain the higher percent of initial ammonia content. Since the layer manure samples from the fall trial were collected from stored manure piles, it is possible that the manure had gone-through a passive composting process entailing to the loss of ammonia nitrogen. In contrast, the breeder and broiler manure samples were collected from fresh manure piles for both trials with similar initial ammonia contents. Results obtained from averaging of the four replicates in each treatment are shown in Table 4.2; similar emission pattern to the spring 2005 trial was evident in the fall 2005 trial (Figure 4.7), with the standard error (SE) bars that represent a 95% confidence interval (CI) for the data. The ammonia emissions were significantly different (p < 0.001) between the various types of poultry manure over the trial period of 21 days after land application. Although they varied in the bulk amount of emissions over the 21 day period, all four types of poultry manure exhibited similar patterns of emissions with the most ammonia being emitted over the first few days and tapering off thereafter, as expected. Table 4.2 Daily ammonia emission rates associated with the land application of the four types of poultry manure - fall trial Days after land spreading Ammonia Emission Rate, mg/d Breeder Broiler Layer Turkey 1 1005 654 449 234 2 175 195 77 62 7 23 28 9 21 14 19 22 15 12 21 9 3 8 5 24 After 21 days, there were no observed differences in grass heights between the treatments, or between the plot areas versus outside grass area. Analysis of grass samples also confirmed that the differential uptake of ammonia nitrogen by the grass is negligible. The ammonia emission rates were then expressed as a fraction of the initial amount of ammonia- nitrogen present in the manure, as demonstrated in Figure 4.8. These profiles1-suggested that the percent ammonia emissions were significantly different (p < 0.001) between the various types of poultry manure 2, 7 and 21 days after land application. After the first two days, breeder manure emitted the most emissions (54%), followed by broiler (41%), layer (26%), and then turkey (20%). This trend is consistent until the end of the trial on day 21; breeder manure had emitted the most emissions (85%), followed by broiler (70%), layer (40%) and turkey (26%). The lower percent ammonia emission of layer manure and turkey manure could be partially attributed to the characteristics of the manure at collection. There is a positive correlation between ammonia emission and pH (r = 0.86), while ammonia emission is again negatively correlated with TN (r = -0.92) for the first 5 hours after land application. Hence, the lower percent ammonia emission from layer and turkey manure could be partially attributed to the pH of the manure at time of application; breeder and broiler manure had a pH around 8.8, compared to layer and turkey manure was 7.9 and 5.9, respectively. The pH affects the equilibrium of NH4 + and NH3. Specifically, the increase in pH increases the concentration of ammonia, allowing for greater volatilization. However, the release of ammonia from the manure increases the acidity by shifting the equilibrium from ammonium ion to ammonia, in turn slowing the release rate of ammonia. 25 Ammonia emission following land application of various types of poultry manure CO C E re 1200 1000 800 600 400 200 0 3 5 7 10 14 Days after land application I Breeder • Broiler • Layer • Turkey 18 21 Figure 4.7 Ammonia emission rates for the various types of poultry manure - fall 2005 trial 100 80 Percent ammonia emission over 2, 7 and 21 days following land application of poultry manure HI x 60 Z 40 .2 o 2 20 • 21 day % average NH3 emission • 7 day % average NH3 emission • 2 day % average NH3 emission Breeder Broiler Layer Type of poultry manure Turkey Figure 4.8 Percent ammonia emission - fall 2005 trial 4.4 Spring 2006 Trial As depicted in Figure 4.9, a similar temporal pattern of emissions was again apparent for the spring 2006 trial. Unlike the previous trials, turkey manure exhibited a significantly different ammonia emission pattern with a loss less than 20% ammonia during the first three days, with peak emission rate of 220 mg d" m" on day 1; subsequently emission declined but then rose to 600 mg d" m" towards the end of the 3-week trial period. This phenomenon is in contrast to other manure types, with most ammonia being emitted over the first few days and tapering off thereafter. The relatively low emissions of turkey manure in the first 3 days in the fall 2005 and spring 2006 trials may be due to its lower manure pH. In the 2006 trial, emission from turkey manure exceeded the other manures on days 16 and 22, probably due to release of ammonia, which might have been accelerated if the manure had been moistened. Other manures tended to have higher pH favoring early release of ammonia. The percent ammonia emissions relative to the initial amount of NH3 -N present in manure were significantly different (p < 0.001), between the various types of poultry manure 2, 8 and 22 days after land application. The ammonia emission rates were then expressed as a fraction of the initial amount of ammonia- nitrogen present in the manure, as demonstrated in Figure 4.10. The percent ammonia emissions relative to the initial amount of N H 3 - N present in manure were significantly different (p < 0.001), between the various types of poultry manure 2, 8 and 22 days after land application. A summary of the cumulative percent total loss of NH3 (relative to total loss at the end of the trial period) after 1, 2, 3 and 7 days after manure application is presented in Table 4.2 Such information would be useful in guiding the timing and abatement value of incorporating manure after spreading. On average, the ammonia losses on day 1 were 48%, 41%, 38% and 29% for breeder, broiler, layer and turkey manure, respectively; and by day 7, the cumulative total ammonia losses reached 83%, 81%, 80% and 67% for these four types of manure. Rodhe and Karlsson (2002) found that incorporation within 4 hours of manure spreading could cut ammonia losses by 50%. Chambers et al. (1999) had also pointed out that rapid incorporation of the manures following land spreading would reduce ammonia emissions by 35-63%. 27 Table 4.3 Cumulative percent total loss of ammonia over days 1,2,3 and 7 after the land application of manure Type of manure % total loss Day 2, % total loss Day 3, % total loss Day 7, % total loss Spring 2005 Trial (manure types)/ Summer 2005 Trial (grass heights) breeder 40 57 . 64 . broiler spring summer 45 45-54 . 66 56-66 73 65-75 89 82-90 layer 24 52 67 83 turkey 47 68 76 89 Fall 2005 Trial breeder 52 66 74 83 broiler 42 61 67 82 layer 50 63 70 82 turkey 30 41 55 70 Spring 2006 Trial breeder 53 64 69 83 broiler 36 44 50 72 layer 39 52 58 76 turkey 11 14 18 42 It should be noted that the turkey manure used in all trials of this project had higher nitrogen contents (6.0-7.5% d.b.) than previously reported (4.0-5.0%) d.b.) by the BC Sustainable Poultry Farming Group (BCMAFF 1997). In contrast, the measured nitrogen contents of other manure types (breeder, broiler and layer) were similar to the previously reported values. Ultimately, the freshness of the manure is measured by the TN, T A N and moisture content; for manure that has been kept in storage over a long period, its TN, T A N and moisture will be lower. 28 Ammonia emission following land application of various types of poultry manure Ti l -i l - T h If fcTTl if frf 4 5 6 Days After Application I Breeder B Broiler • Layer • Turkey | Figure 4.9 Ammonia emission rates for the various types of poultry manure - spring 2006 trial Percent ammonia emitted over 2, 8 and 22 days following land application of poultry manure 80.0 Breeder Broiler Layer Turkey Treatment Figure 4.10 Percent ammonia emission - spring 2006 trial 29 4.5 Effects of Temperature and Humidity Many factors can affect the NH3 volatilization rate and amount from the soil; air temperature, humidity, and wind speed are positively correlated with NH3 loss. Estimates of the total percent of NH4-N lost during waste storage, or after land application, vary from 10 to 100% of the NH4- N fraction (Mahdi et al., 2002). This wide range in measured NH3 losses rejults^from differences in waste composition, climatic conditions, soils, application methods, and the techniques used for measuring NH3 fluxes. They found that high temperatures and wind speeds increased NH4-N loss during effluent application and from the soil. It was not possible to separate the combined effect of both parameters on NH4-N loss from sprinkler and soil. However, it was evident that higher air temperatures increased NH4-N loss during May and November of 1999, and high wind speeds increased NH4-N loss during 3 r d and 6 th of May 1999 (Al-Kaisi et. al. 2002). Their results show the percentage of NH4-N loss was affected by both temperature and wind speed changes. Temperature was consistently higher during the spring 2005 trial versus the fall 2005 trial. The difference in temperatures ranged from 4.7°C to 12.5°C in the first 48 hours after manure spreading, when ammonia emissions were the highest, as illustrated in Figure 4.11. Relative humidity was also observed to be lower (Figure 4.12) for the spring trial (50-100%) versus the fall trial (80-100%). It shall be noted that spring 2006 was also warmer than fall 2005. Ammonia emissions are expected to be higher in spring and summer times with higher ambient and soil temperatures. Daily ammonia emission rates, as previously displayed, were higher for all types of manure in both spring trials than the fall 2005 trial, and the maximum daily emission rates were seen in the summer trial. Since the manure application rates were different for the spring and summer 2005 trials versus the fall 2005 and spring 2006 trials, a comparison was made between the trials, based on ammonia emitted as a fraction of the initial amount of ammonium-nitrogen present in manure. Results then indicated that, despite the variations of ammonium-nitrogen out of total nitrogen content in the manure, the fraction of ammonia emitted was consistently greatest in fall 2005 for the breeder, broiler and layer manure. Likewise, the fraction of ammonia emitted from the broiler manure used in the summer trial was also close to that of the fall trial. Turkey manure had the 30 lowest emission in fall 2005, but this may rather be attributed to its pH value lower than 6, which is not favorable for ammonia volatilization. Temperatures for Spring and Fall Trials (first 7 days) 0 50 100 150 Time (hours since application) Spring Temperature — a — Fall Temperature Figure 4.11 Temperature measurements for the spring and fall trials Relative Humidity (%) for Spring and Fall Trials (first 7 days) 60 80 100 120 Time (hours since application) • Spring Rel Hum (%) — a Fall Rel Hum (% Figure 4.12 Relative humidity measurements for the spring and fall trials 31 4.6 Ammonia Emission Factors A summary of the values and seasonal emission factors based on U A N and T N are depicted in Table 4.4 and Table 4.6. The ammonia emission factors derived demonstrate all treatments did not exceed the initial amount of T A N present in manure for all trials and variations with season and among the various types of poultry manure. Overall, the magnitudes of the emission factors based on percent of total nitrogen are comparable to findings from othefWsearch studies, for instance, 0.033-0.24 (Huijsmans et. al. 2003) and 0.135 for broiler litter without incorporation (Misselbrook et. al. 2005). Turkey manure had the lowest emission in fall 2005; this may be attributed to its pH value being lower than 6, which is not favorable for ammonia volatilization. Layer manure exhibited the most consistent trend during all trials. The revised ammonia emission factors as presented in Table 4.5, obtained by taking the average values of the emission factors from all trials, were then obtained on the basis of the average values of the seasonal variations. For comparison, the current values of emission factors adopted by Environment Canada (2005) are also shown in Table 4.5, and emission factors used by other countries are shown in Table 2.1. For the two major types of poultry - broiler and layer, current emission factors of 0.11 and 0.15 are very close to the updated values of 0.12 and 0.16, respectively. A large difference was induced for the turkey manure, with current value and revised value of emission factor being 0.38 and 0.11, respectively. The revised value of 0.11 is similar to broiler manure, as both types of poultry use a lot of bedding materials. It may also be attributed to the high nitrogen content of the turkey manure used in all trials of this project (6.0- 7.5% d.b.), as compared to nitrogen contents of 4.0-5.0% d.b. previously reported by the Sustainable Poultry Farming Group (SPFG) (BCMAFF 1997). By comparison, the measured nitrogen contents of other manure types were all similar to the previously reported values - for breeder, (2.9-4.3%) versus (SPFG 2.6-3.6%); for broiler, (2.7-4.7%) versus (SPFG 4.6%) and for layer/pullets, (4.6-6.3%) versus (SPFG 4.1-6.6%). These emission factors are pertinent to "uncontrolled emissions", and are reported as "the amount of NH3 -N volatilized as a percentage of total N in poultry manure". Preliminary work on uric acid analysis was performed with an aim to delineate whether "ammonia emissions from land spreading of poultry manure can persist for many weeks because 32 of the slow conversion of uric acid to urea, and hence ammonia (Misselbrook et. al. 2000)", or, "most of the uric acid would have been converted to ammonium within a few days of the in-barn storage of the manure (Nahn 2005)". The all manure used in the experiments were acquired from commercial poultry barns, either fresh, in-barn storage, or stored as covered piles outdoor. The ammonia emission measurements and patterns suggested that, regardless of the age of manure, the latter scenario was likely more applicable to the findings from this study—-***— If the ammonia emission factors are to be expressed relative to uric-acid plus ammonium- nitrogen (UAN) content rather than total nitrogen (TN) content of poultry manure, then the emission factors could become substantially different for the broiler, layer and turkey manure, as evident in Table 4.4. It shall be noted, however, that most of the U A N values were adapted from Nicholson et al. 1996, except for the spring 2006 data. Although emission factors based on U A N might be more representative of poultry manure as an effective nitrogen source, the values estimated here need to be verified with the analysis of uric acid content for many more samples in the future. The major errors would lie with the ammonia concentration measurements by the flow injection analyzer. The device occasionally produced results from the wrong sample; however, all samples were analyzed repeatedly until the results were consistent. Another error is in the collection of acid traps containing ammonia, where most or all of the acid contents was found to have evaporated from its container. In these cases, other replicates were used to compensate for the loss in data. Therefore, with multiple replicates and repeated analyses, the values are considered fairly accurate, as reflected in the standard deviations of the emission factors shown in Table 4.4 or Table 4.6. 33 Table 4.4 Ammonia emitted as a fraction of various forms of initial nitrogen Spring 2005 Fall 2005 Spring 2006 breeder kgNH3kg-' initial TAN kg NH 3 kg"1 initial TN 0.35 ± 0.03 0.09 ±0.01 0.85 ± 0.05 0.30 ±0.02 0.71 ± 0.05 0.20 ±0.01 broiler kgNH3kg"' initial TAN kg NH 3 kg"1 initial TN 0.57 ±0.18 0.12 ±0.03 0.70 ± 0.07 0.12 ±0.01 0.46 ±0.10 0.09 ±0.02 layer kg NH 3 kg"' initial TAN kgNH3kg"' initial TN 0.37 ±0.10 0.23 ± 0.06 0.40 ± 0.04 0.06 ±0.01 0.33 ± 0.06 0.18 ±0.03 turkey kg NH 3 kg' initial TAN kg NH 3 kg"1 initial TN 0.25 ± 0.04 0.08 ± 0.02 0.22 ± 0.02 0.10 ±0.01 0.65 ± 0.09 0.14 ±0.02 NH 3-N: ammonium-nitrogen; UAN: uric-acid plus ammonium-nitrogen; TN: total nitrogen Table 4.5 Comparison of current values and revised values of ammonia emission factors* Current values kg NHj/initial kg N H 3 Revised values kg NHj/initial kg N H 3 Current values kg NHj/initial kg TN (based on TN) Revised values kg NHj/initial kg TN (based on TN) breeder 0.50 0.64 0.15 0.20 broiler 0.50 0.59 0.11 0.12 layer 0.50 0.37 0.15 0.16 turkey 0.50 0.37 0.38 0.11 * Current values: adopted by Environment Canada (2006); Revised values: derived from this study 34 Table 4.6 Manure Analysis and Application Rates Type of manure Application rate, kg/m2 Moisture content, % w.b. Total nitrogen, % d.b. Ammonia- N, % d.b. pH Emission Factor kgNH 3/kg initial TN Emission Factor kg-NWkg initial-TAN Spring 2005 Manure Types Trial breeder 2.08 33.3 2.98 0.72 8.4 0.09 ±0.01 0.35 ± 0.03 broiler 2.79 36.7 2.67 0.57 8.5 0.12 ±0.03 0.57 ±0.18 layer 1.26 79.5 6.26 3.88 6.5 0.23 ± 0.06 0.37 ±0.10 turkey 0.74 41.6 7.35 2.33 8.4 0.08 ± 0.02 0.25 ± 0.04 Summer 2005 Grass Heights Trial broiler 2.79 36.7 2.67 0.57 8.1 0.14 ±0.03 0.64 ±0.13 Fall 2005 Manure Types Trial breeder 0.56 23.0 2.89 1.22 8.8 0.30 ± 0.02 0.85 ±0.05 broiler 0.68 32.1 3.06 0.52 8.9 0.12 ±0.01 0.70 ± 0.07 layer 0.30 13.4 5.90 0.82 7.9 0.06 ±0.01 0.40 ± 0.04 turkey 0.30 29.0 7.53 1.84 5.9 0.10 ±0.01 0.22 ± 0.02 Spring 2006 Manure Types Trial breeder 0.52 31.7 4.26 1.20 7.3 0.20 ±0.01 0.71±0.05 broiler 0.41 22.1 4.73 0.90 7.5 0.09 ± 0.02 0.46±0.10 layer 0.71 53.7 4.55 2.53 7.3 0.18 ±0.03 0.33±0.06 turkey 0.36 29.6 5.95 1.26 6.7 0.14 ±0.02 0.65±0.09 w.b.: wet basis d.b.: dry basis 35 CHAPTER V - Conclusions and Recommendations 5.1 Conclusions Based on the field trials performed under contrasting conditions in 2005 and 2006, total ammonia emissions based on TN and T A N were significantly different between manure types (p < 0.005), but the ranking varied with trial. Other than the turkey manure used in spring 2006, the highest emission rate occurred immediately proceeding application, then gradually declining in the 2-3 weeks period towards the end of the trial. By cultivating the manure within 24 h, emission reduction of over 50% can be achieved, but a delay of 48 hrs would usually lead to a reduction of only 35-40%. As expected, ammonia emission rates were generally greater in both of the spring trials compared to the fall trial. In spite of the differences of T A N content versus T N content in the four types of manure, ammonia emitted as a fraction of the initial amount of T A N present in manure was consistently greatest in fall 2005 for the breeder, broiler and layer manure. However, turkey manure had the lowest emission in fall 2005; this may be the result of its pH value being lower than 6, which is not favorable for ammonia volatilization. Within the monitored period, the initial amount of NH3- N in the manure for all treatments was never exceeded by the cumulative ammonia emission, suggesting that the conversion of uric acid to ammonia after land application might not be significant for the manures used in these trials. Based on the spring and fall trials, ammonia emissions were significantly different between the manure types (p < 0.005). For the summer trial, ammonia emitted as a percent of initial NH3 -N was 50% for the high grass height of 275 mm, as compared to 65-70% for the other grass canopies (25-175 mm). However, the differences in emission rates were not statistically significant (p > 0.1). The summer trial examining the effects of grass height on emissions revealed that ammonia- nitrogen uptake increased with grass height; however, wind speed was also identified to be the major factor, as a taller grass canopy led to less turbulence in the boundary layer, reducing ammonia diffusion and further ammonia volatilization from the soil surface. Statistically, there 36 was no significant difference (p > 0.10) in ammonia volatilization between treatments of 25mm, 75mm, 175mm and 275mm of orchard grass. The quantity of ammonia emitted within 24 hours (day 1), expressed as a percentage of the total ammonia emission over the duration of each trial, was found to be 48%, 41%, 38% and 29% for breeder, broiler, layer and turkey manure, respectively. Moreover, most of-4he emission in the first day took place within the first 2-5 hours after land application of manure. By day 7, the cumulative total ammonia losses reached 83%, 81%, 80% and 67% for these four types of manure. This information would prove useful in guiding the timing and abatement value of incorporating manure after spreading. The ammonia emission factors derived from the experimental results of this study demonstrate variations among the various types of poultry manure. For the two major types of poultry - broiler and layer, current emission factors of 0.11 and 0.15 adopted by Environment Canada are very close to the updated values of 0.12 and 0.16, respectively. However, substantial difference was induced for the turkey manure, with current value and revised value of emission factor being 0.38 and 0.11, respectively. The revised value of 0.11 is similar to broiler manure, as both types of poultry use a lot of bedding materials. It may also be attributed to the high nitrogen content of the turkey manure used in all trials of this project. The EC guidelines for reporting ammonia emission factors are taken from the Criteria Air Contaminants guidebook, an unpublished document (Environment Canada, 2006). Upon analyzing the data and information from, the following assumptions were realized: a) The NH3:TN ratio is 0.62, which means, ammonium-nitrogen constitutes 62% of total nitrogen in excreted turkey manure. b) 50% of the available nitrogen (as NH3-N) initially present in manure is volatilized after land application of manure These assumptions are not applicable to the results obtained in the present study. Firstly, manure analysis indicates that the NH3:TN ratio for turkey manure is 0.21-0.32 (Table 3.1), which is substantially lower than 0.62. Secondly, the amount of NH3-N volatilized is 37% of the NH3-N 37 initially present in turkey manure (Table 4.5), rather than the assumed value of 50%. This is the reason for the discrepancies between the two values, 0.38 versus 0.11, when ammonia emission is expressed in [kg NH3/initial kg TN] or [%TN]. It is also realized that the Environment Canada values of the emission factors are numerically the same in units of [kg-NH3/initial kg-N] or [kg NH3/animal/year]. Environment Canada could have adopted these values with reference to European data (Table 2.1) (Kuczynski et al 2005). Furthermore, it would suggest that the manure nitrogen excretion rate was assumed by EC to be [1.0 kg N/bird/year], as the conversion factor between the two units. This assumed conversion factor is compatible with those reported in the literature for turkey manure, being [1.1 kg N/bird/year] (USEPA, 2005) and [0.9 kg N/bird/year] (Ohio State University, 2007), for 6 cycles of production per year and 37 days per cycle, typical in the BC poultry industry. Nevertheless, this assumed value is substantially different for layer and broiler manure, since values of 0.22- 0.29 kg N/bird/year and 0.12-0.25 kg N/bird/year are given by USEPA (2005) and OSU (2007). As mentioned earlier, poultry manure may be applied to vegetable crops, grass and cereals in BC. However, this study was done in parallel with a project (at Agassiz Research Station) that concerns the land application of dairy manure, which is largely for grass. From the observations and conclusions of this study, ammonia volatilization was greater with breeder and broiler manure. If possible, it is therefore more efficient to utilize the nutrients in layer and turkey manure as fertilizer. Using additives in the manure to reduce the pH would reduce ammonia emissions, which means, more nitrogen would be available for plant growth. Farmers can follow the application guidelines similar to those used in this study. However, the manure pH will vary from farm to farm. When making recommendations to Environment Canada on the effects of the various factors, the effect of pH will be singled out as the dominant factor, as it seems to over- ride the effects of temperature. Since pH was found to be the dominant factor, it is possible to predict whether ammonia emission may be higher or lower based on the pH value of manure. However, further trials may be required to obtain more data points in order to develop a regression equation with high R2 value. A lower wind velocity would also reduce ammonia volatilization; hence, measures taken to limit wind speeds at the soil-manure surface could also contribute to reduced nutrient losses. 38 5.2 Recommendations Poultry manure samples collected from farms for this study did not always possess characteristics similar to manure found most common in the area; more specifically, the moisture content and total nitrogen of the manure may vary between barns utilizing different equipment and operations. However, it was difficult to find farmers with available manure; either manure inside the barn had yet to be transferred to a storage facility, or the manure had been removed from storage to disposal or application. For consistency, all manures should be collected either during the housing or storage stage from poultry farms representative of those most commonly found in the Lower Fraser Valley. The air velocity inside the wind tunnel is generally higher than regular wind speeds; however, the blower was already set at the minimum setting. A device that could simulate lower wind speed would likely yield ammonia emission factors most representative of British Columbia. Inside Tygon tubes, condensation will remove ammonia from the air sample being drawn into the acid trap. Whenever moisture was observed inside a tube, it was immediately replaced by a dry duplicate. Ideally, the tubes should be free of moisture at all times during experimentation. Evaporation during hot summer days occasionally caused the acid traps to run dry; larger volume of acid, ventilation of the container in which the acid trap sits, or frequent shift changes of the sample would eliminate the chance of losing data. The flow injection analyzer often had difficulty at reading the concentration of ammonia in the sample. A more consistent method of analysis can potentially reduce the error margins. It was found that manure pH is a dominate factor in estimating ammonia volatilization. In future studies where the main objective is to limit emissions of ammonia from poultry manure, additives of acid or base should be used to manipulate manure pH as a primary variable in the experiments. In comparison with this study, the manure types and grass heights would be kept constant, as well as all other controlled variables. 39 REFERENCES Al-Kaisi, M . M . and R.M. Waskom. 2002. Nitrogen management - estimating ammonia loss from sprinkler-applied swine effluent. Agron. J. 94: 1156-1162. Anderson, N. , Strader, R. and Davidson, C. 2003. Airborne Reduced Nitrogen: Ammonia Emissions from Agriculture and Other Sources. Environmental International v. 29 277-286. Anon. 2003. Ammonia fluxes within broiler litter and layer manure management systems. Final report of project WA0651 for the Department for Environment, Food and Rural Affairs, UK. 39. Battye, W., V. P. Aneja and P. A. Roelle. 2003. Evaluation and improvement of ammonia emissions inventories. Atmospheric Environment 37(27): 3873-83. Bouwman, A.F. , L. J. M . Boumans and N. H. Batjes. 2002. Estimation of global NH3 volatilization loss from synthetic fertilizers and animal manure applied to arable lands and grasslands. Global Biogeochemical Cycles 16(2): 1-15. British Columbia Ministry of Agriculture, Fisheries and Food (BCMAFF). 1997. Environmental guidelines for poultry producers in British Columbia. (Ed. R. van Kleeck). 94. Chinkin, L. R., Ryan, P.A., C, D.L. 2003.Recommended Improvements to the C M U Ammonia Emission Inventory Model for Use By LADCO. Sonoma Techonology Inc. Revised Final Report 902350-2249-FR2: 23-29. EMEP/CORINAIR Atmospheric Emission Inventory Guidebook (3rd Ed.). 2002. Copenhagen, Denmark, http://reports.eea.eu.int/ EMEPCORINAIR3/en/ Environment Canada. 2005. Criteria Air Contaminants (CAC) Section, Pollution Data Division. Unpublished report. Sandjay Girdhar, personal communication. Goebes, M.D., R Strader and C Davidson. 2003. An ammonia emission inventory for fertilizer application in the United States. Atmospheric Environment 37(18): 2539-50. Guiziou, F. and F. Beline 2005 In situ measurement of ammonia and greenhouse gas emissions from broiler houses in France. Bioresource Technology 96(2): 203-207. Hansen, M.N., Sommer, S.G. and Madsen, N.P. 2003. Reduction of Ammonia Emission by Shallow Slurry Injection: Injection Efficiency and Additional Energy Demand. Journal of Environmental Quality v. 32(3) 1099-1104. 40 Harrison, R. and Webb, J. 2001. A Review of the Effect of N Fertilizer Type on Gaseous Emissions. Avances In Agronomy v. 73 67-108. Huijsmans, J.F.M., Hoi, J. M . G., and Vermeulen, G. D. 2003. Effect of application method, manure characteristics, weather and field conditions on ammonia volatilization from manure applied to arable land. Atmospheric Environment 37(26): 3669-80. Kaffka, S.R. and V. R. Kanneganti. 1996. Orchard Grass Response to Different Types, Rates, and Application Patterns of Dairy Manure. Field Crops Research 47 (1996) 43-52. Krupa, S.V. 2003. Effects of Atmospheric Ammonia (NH3) on Terrestrial Vegetation: A Review. Environmental Pollution v. 124(2) 179-221. Kuczynski, T., J. Webb, U. Dammgen and A. Myczko. (Eds). 2005. Emissions form European Agriculture. Wageningen Academic Publishers. The Netherlands. 384. Larsson, L. Ferm, M . , Kasimir-Klemedtsson, A. and Klemedtsson, L. 1998. Ammonia and Nitrous Oxide Emissions From Grass and Alfalfa Mulches. Nutrient Cycling in Agroecosystems v. 51(1)41-46. Lefebvre, A., W. Eilers and B. Chunn. (Eds.). 2005. Environmental Sustainability of Canadian Agriculture: Agri-Environmental Indicator Report Series - Report #2. Agriculture and Agri-Food Canada, Ottawa, Ontario. Liang, Y.,. Xin, H., Wheeler, E. F., Gates, R. S., Li , H., Zajaczkowski, J. S., Topper, P. A., Casey, K. D., Behrends, B. R., Burnham, D. J., Zajaczkowski, F. J. 2005. Ammonia emissions from U.S. laying hen houses in Iowa and Pennsylvania. Transactions of the A S A E v. 48 no. 5 (September/October 2005) 1927-41. Lockyer, D. R., Pain, B.F., Klarenbeek, J.V. 1989. Ammonia emissions from cattle, pig and poultry wastes applied to pasture. Environmental Pollution v. 56 no. 1 (1989) 19-30. Mahdi M . Al-Kaisi and Reagan M . Waskom (2002). Nitrogen Management - Estimating Ammonia Loss from Sprinkler-Applied Swine Effluent Agron. J. 94:1156-1162 McGinn, S.M., Janzen, H.H. 2003. Ammonia Sources in Agriculture and Their Measurement. Canadian Journal of Soil Science v. 78(1) 139-148. Misselbrook, T.H., F. A. Nicholson and B. J. Chambers. 2005. Predicting ammonia losses following the application of livestock manure to land. Bioresource Technology 96(2): 159-168. 41 Misselbrook, T.H., T. J. Van Der Weerden, B. F. Pain, S. C. Jarvis, B. J. Chambers, K. A. Smith, V. R. Phillips and T. G. M . Demmers. 2000. Ammonia emission factors for U K agriculture. Atmospheric Environment 34(6): 871-880. Nahm, K . M . 2005. Factors influencing nitrogen mineralization during poultry litter composting and calculations for available nitrogen. World's Poultry Science Journal 61: 238-255. Nicholson, F.A., B. J. Chambers and A.W. Walker. 2004. Ammonia emissions from broiler litter and laying hen management systems. Biosystems Engineering 89(2): 175-185. Nicholson, F.A., B.J. Chambers and K.A. Smith. 1996. Nutrient composition of poultry manures in England and Wales. Bioresource Technology 58: 279-284. Ohio State University. 2007. Poultry manure management and utilization problems and opportunities. Bulletin 804. (internet access Sept 2007 http://ohioline.osu.edu/b804/804_3.html) Patni, N.K. 2004. Scoping Study for Improvement of Emission Factors and Emission Inventories of Ammonia from the Agricultural Sector in Canada, Final Report. Prepared for Environment Canada, Criteria Air Contaminants Division, Pollution Data Branch 61. Rodhe, L. and S. Karlsson 2002. Ammonia Emissions from Broiler Manure- Influence of Storage and Spreading Method. Biosystems Engineering 82(4): 455-462. Schlesinger, W.H. and Hartley, A .E . 1992. A Global Budget for Atmospheric NH3. Biogeochemistry v. 15(3) 191-211. Sharpe, R.R., H. H. Schomberg, L. A. Harper, D. M . Endale, M . B. Jenkins and A. J. Franzluebbers. 2004. Ammonia Volatilization from Surface-Applied Poultry Litter under Conservation Tillage Management Practices. Journal of Environmental Quality 33: 1183-88. Siefert, R. L., Scudlark, J.R., Potter, A .G. , Simonsen, K.A. , Savidge, K.B. 2004. Characterization of Atmospheric Ammonia Emissions from a Commercial Chicken House on the Delmarva Peninsula. Environmental Science & Technology v. 38 no. 10 (May 15 2004) 2769-78. USEPA. 2005. National Emission Inventory: Ammonia Emissions from Animal Agricultural Operations. Revised Draft Report. 212. Wulf, S., M . Maeting and J. Clemens. 2002. Application technique and slurry co-fermentation effects on ammonia, nitrous oxide, and methane emissions after spreading. I. Ammonia volatilization. Journal of Environmental Quality 31:1789-1794. Zebarth, B.J., Paul, J.W. and Van Kleeck, R. 1999. The Effect of Nitrogen Management in Agricultural Production on Water and Air Quality: Evaluation on a Regional Scale. Agriculture, Ecosystems & Environment v. 72(1) 35-52. 42 APPENDICES Appendix A - Sample Calculations Ammonia emission of a shift Equation 1 E = (C 0 Where: E ammonia emission rate based on sub-sample tunnel air, [mg per interval] Co concentration of ammonia at blower intake [mg/L] Ci concentration of ammonia at tunnel intake [mg/L] V volume of acid trap solution [L] R ratio of actual airflow rate to the sub-sample airflow rate = v A/Q V rotary anemometer speed anemometer wind speed [m/s] A tunnel cross sectional area [m2] Q sub-sample flow rate [m3/hr] From spring 05 first replicate of turkey manure, shift one on day one. Given: C 0 = 1.861 mg/L NH 3 -N , Q = 0.351 mg/L, V = 0.029575 L Q = 0.1494 m3/h, A = 0.01675 m 2, v = 13.5 m/s R = (13.5 m/s)( 0.01675 m2)(3600 s/h)/(0.1494 m3/h) R = 5449.6 E = (1.861 mg/L - 0.351 mg/L)(0.029575 L)(5449.6) E = 1035.8 mg per interval -C0VR Ammonia emission factor From spring 05 of turkey manure, all shifts over the trial period for all replicates. Given: The duration of the spring 05 trial is 16 days The mass of ammonia emitted for the 4 replicates are 2903.4, 2421.0, 2129.2, 2743.5 mg. From Table 3.1, the application rate, moisture content, percent total nitrogen (dry basis) and percent ammonia (dry basis) are 0.74 kg/m2, 41.6%, 7.35%, 2.33%, respectively. Total nitrogen in the manure applied = (0.74 kg/m2)(l-0.416)(0.0735)(0.5m*2.0m) = 0.318 kg or 31,800 mg Average of total ammonia emitted = (2903.4 + 2421.0 + 2129.2 + 2743.5)(4)"' of turkey manure = 2549.3 mg Emission Factor for turkey in spring = (2549.3 mg)(31,800 mg)"1 05 in kg-NH3-N/kg-initial-N = 0.080 kg N H 3 kg"1 initial TN Total ammonia in the manure applied = (0.74 kg/m2)(l-0.416)(0.0233)(0.5m*2.0m) = 0.100 kg or 10,000 mg Emission Factor for turkey in spring = (2549.3 mg)(31,800 mg)-1 05 in kg-NH3-N/kg-initial-N = 0.25 kg N H 3 kg"1 initial T A N A table containing spring 05 emission data in mg for each shift and day for all treatments and replicates are shown below, where treatment 1 through 4 are turkey, broiler, breeder, and layer, respectively; treatment and replicate numbers are abbreviated to T and R (T1R2 referring to replicate 2 of treatment one, for example). A second table contains the total ammonia emission of each shift and day average between all replicates of each treatment and the sum of shifts taken within each day. The third table contains the daily ammonia emission derived from the sum of shifts from each day or days. 44 Ammonia emission from each shift - spring 2005 Day 1 Shift 2 3 4 5 7 8 9 10 12 16 16 days 2 days |mo| [mo| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 25 F B I F S I Mel6 Mel T1R1 1035.760 162.238 308.136 1227.442 364.714 120.434 75.920 68.582 21.998 5.928 56.740 120.298 91.570 48.079 49.998 14.040 11.990 0.000 57.805 25.774 31.578 2.466 1.903 2903.394 2757.838 T2R1 1495.189 412.785 836.877 578.645 596.887 208.698 136.489 123.155 31.541 54.459 194.491 245.168 159.390 76.324 88.870 24.815 13.310 18.203 148.026 78.419 67.409 45.404 13.830 5648.387 5238.969 T3R] 994.778 186.932 383.424 221.064 326.156 144.909 100.394 90.199 27.548 47.325 125.708 199.422 153.447 69.880 57.727 40.031 73.588 36.965 144.598 69.039 50.146 33.468 39.023 3615.774 3128.914 T4R1 267.820 99.230 523.259 494.907 316.735 262.947 119.529 133.934 64.624 68.484 104.566 63.842 42.772 12.591 20.518 28.754 21.268 20.404 37.653 37.432 7.402 33.419 65.572 2847.662 2595.758 T3R2 871963 253.027 498.906 285.350 402.048 124.808 82.555 66.261 51.510 50.336 146.701 227.847 154.129 62.894 60.917 34.767 45.845 51.056 162.599 77.842 75.908 47.015 50.763 3886.048 3340.252 T4R2 347.991 209.166 579.481 570.416 598.001 316.812 146.023 150.488 38.532 59.163 125.098 134.950 25.963 32.730 12.662 24.875 14.015 13.286 32.385 17.071 31.263 15.648 48.762 3544.782 3347.476 T1R2 567.777 190.586 373.798 170.163 350.928 102.153 50.306 48.871 5.699 18.249 51.769 111.020 79.036 42.568 41.313 18.335 13.826 38.837 62.517 32.106 34.099 7.134 9.920 2421.011 2204.236 T2R2 1071.126 415.415 598.775 459.688 489.142 185.726 144.645 79.624 49.522 50.151 127.333 221.656 145.600 70.188 61.537 24.166 28.180 26.683 120.814 48.271 72.005 27.884 41.045 4559.175 4170.125 T4R3 141.804 203.109 296.070 468.490 600.557 404.709 245.900 183.460 60.755 79.053 158.724 157.263 70.986 18.208 64.122 24.085 42.498 8.482 45324 14.084 14.266 31.942 44.825 3378.715 3153.211 T1R3 279.842 250.061 303.557 180.567 327.907 129.919 81.038 60.895 15.528 12.291 48.331 91.501 84.396 60.800 17.689 20.169 11.925 13.058 50.020 35.898 27.617 26.238 0.000 2129.248 1944323 T2R3 1839595 812.953 748.513 933.876 800.874 341.734 144.051 181.463 67.052 48.818 338.895 486.071 294.568 139.969 67.005 51.457 55.881 83.424 310.332 126.603 188.190 71.149 83.126 8215.599 7245.437 T3R3 633.012 311.719 330.240 291.556 316.087 156.076 128.402 83.031 45.904 63.636 289.036 170J49 114.473 54.801 47.442 25.166 57.679 40.949 95.036 47.251 31.724 68.886 51.643 3454.097 3035.763 T2R4 1060.442 471.548 486.023 423.651 507.111 203.980 163.915 102.541 17.891 10.109 103.926 239.033 127.782 67.853 40.533 14.556 13.191 7.016 50.818 27.598 3.429 5.972 64.673 4213.591 4026339 T4R4 242.860 231.613 396.744 585.719 586.904 436.976 216.520 218.763 91.608 85.981 153.934 99.980 77.423 39.536 28.362 36.335 57.156 196.465 331.979 151.597 277.081 158.170 384.567 5086.275 3492.923 T3R4 576.517 262.904 316.384 240.297 261.701 176.286 119.159 62.914 33.843 39.404 125.611 202.792 0.000 65.133 51.415 77.383 65.326 47394 143.664 90.030 106.489 52.721 23.223 3140.589 2534358 T1R4 818.361 256.082 259.794 173.217 341.147 116.604 83388 66J84 12.598 19.063 63.277 129.630 42.085 111.816 44.080 34373 11.810 18.410 67.838 31.909 17.448 2.641 21.506 2743.461 2537.526 Average ammonia emission from each shift - spring 2005 Day 1 2 3 4 5 7 8 9 10 12 16 Shift 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 25 TKY 675.44 214.74 311.32 187.85 346.17 117.28 72.66 61.18 13.96 13.88 55.03 113.11 74.27 65.82 38.27 21.73 12.39 17.58 59.55 31.42 27.69 9.62 8.33 BROIL 1366.59 528.18 667.55, 598.96 598.50 235.03 147.28 121.70 41.50 40.88 191.16 297.98 181.84 88.58 64.49 28.75 27.64 33.83 157.50 70.22 82.76 37.60 50.67 BREED 769.32 253.65 382.24 259.57 326.50 150.52 107.63 75.60 39.70 50.18 171.76 200.10 105.51 63.18 54.38 44.34 60.61 44.09 136.47 71.04 66.07 50.52 41.16 LYR 250.12 185.78 448.89 529.88 525.55 355.36 181.99 171.66 63.88 73.17 135.58 114.01 54.29 25.77 31.42 28.51 33.73 59.66 111.84 55.05 82.50 59.79 135.93 Appendix B - Procedure of Analyses Uric Acid Analysis 1. The poultry manure samples are first weighed then freeze dried for one week to minimize degradation. The sample is weighed again to measure the moisture/dry matter content. 2. Freeze dried samples are ground to lower particle size for better liquid-solid extraction. 3. Uric acid was extracted using 1M NaCC«3 over 24 hours. 4. The solution was centrifuged and 50 ml of the supernatant was obtained for analysis. 5. Reagents from the Bioassay Systems' uric acid assay kit are prepared prior to analysis using a spectrophotometer. 6. The sample is combined with the reagents at the appropriate amount and incubated for 20 to 60 minutes at room temperature. 7. The blank, standard, and samples were transferred to 3 ml cuvettes and the optical density was read at 590 nm. 8. The uric acid concentration of the sample was calculated by the following equation: (10 mg/dL)(OD s a m pi e - ODblankVCODstandiiKl - O D ^ ) where: ODsampie Optical density of the sample; ODbiank Optical density of the blank; and ODstandard Optical density of the standard. Given: ODsampk = 0.490, O D b l a n k = 0, ODstandard = 0.714 U A Concentration = (10 mg/dL)(0.490 - 0)/(0.714 - 0) U A Concentration = 6.86 mg/dL 9. The mass of uric acid content in each sample is found by multiplying the dry matter content with the uric acid concentration. 47 Flow Injection Analyzer (FIA) Analysis 1. Reagents for analyzing ammonia are prepared following the manual provided by the manufacturer. Once prepared, Teflon tube lines, each labelled with the name of the reagent it is meant for, are placed into the appropriate containers to condition the lines using a displacement pump. 2. Prepared samples obtained from acid traps are poured into test tubes-custom to the FIA. Up to 60 samples can be measured every set. 3. The temperature of the FIA is set to 60°C, appropriate for N H 3 analyses. 4. On the computer from which the FIA is controlled, each test tube was labelled according to the shift and tunnel from which the sample originated. 5. Standards and samples are placed into the rack from which sub-samples are drawn. 6. The analyzer then reads the ammonia concentration [mg/L] based on the calibration curve obtained from reading the standards. Manure pH Analysis 1. A sample of manure was weighed to an arbitrary value of 1 gram; the sample was then transferred into a 50 ml test tube. 2. Water was added into the test tube to fill to a volume of 10 ml. 3. The test tube was covered/capped and shaken for 1 minute; the pH of the solution was measured and recorded. 4. Water was again added to volumes of 15, 20, and 25 ml; the sample was again shaken and the pH measured and recorded. 5. A volume of sample versus pH curve was plotted, the linear fit for the 4 data points extrapolated to a water volume of 0 was determined as the manure pH. 6. The average of 3 manure pH values determined by this method was used as the actual manure pH. 48

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