EPA-600/2-76-239 September 1976 Environmental Protection Technology Series PRODUCTION AMD TRANSPORT OF GASEOUS NH3 AND H2S ASSOCIATED WITH LIVESTOCK PRODUCTION lobeit 1 ICirr EkwoBraiBtai Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Ada, Oklahoma 74820 ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into five series. These five broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The five series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY series. This series describes research performed to develop and demonstrate instrumentation, equipment, and methodology to repair or prevent environmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161. ------- EPA-600/2-76-239 September 1976 PRODUCTION AND TRANSPORT OF GASEOUS NH3 AND ASSOCIATED WITH LIVESTOCK PRODUCTION by J. Ronald Miner Agricultural Engineering Department Oregon State University Corvallis, Oregon 97331 Grant No. S-802009 Project Officer R. Douglas Kreis Robert S. Kerr Environmental Research Laboratory Ada, Oklahoma 74820 ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY ADA, OKLAHOMA 74320 ------- DISCLAIMER This report has been reviewed by the Robert S. Kerr Environ- mental Research Laboratory, U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. ------- ABSTRACT Current livestock production techniques release a large variety of volatile organic compounds to the atmosphere. This release results in complaints due to the odorous nature of the compounds and has been identified as a source of sur- face water pollution as these compounds are absorbed from the air. Ammonia has been identified as the compound of greatest concern relative to water pollution and of con- siderable interest relative to odor complaints because of its ease of measurement and its relationship to more odorous gas evolution. Gas sampling and measuring schemes based upon the use of solid absorbents were investigated. The use of an absorbent suspended in a stainless steel screen container which could be exposed in an atmosphere to be sampled showed promise. The large number of volatiles absorbed compounded identifi- cation procedures. Trimethylamine was identified as a nitrogen-bearing volatile of particular odor importance. The evolution of ammonia, hydrogen sulfide, and odorous volatiles was investigated as a function of beef cattle ration. The addition of an essential oil, mint oil, was found to alter the odor of fresh manure by masking. The mint oil odor was carried in the urine. Ammonia evolution from fresh manure was largely from urine. Fecal contri- butions became significant only after considerable decom- position had occurred. A technique was devised for measuring the ammonia evolution rate from surfaces within and associated with livestock production enterprises. Included were barn floor surfaces, corral surfaces, and land to which manure had been applied. This measurement proved to be an accurate reflection of anaerobic biological activity and to provide a quantitative means for comparing treatment procedures designed to minimize volatile material evolution rates. Evolution rates for a variety of surfaces associated with livestock production enterprises were measured. This report was submitted in fulfillment of Project Number S-802009 under the partial support of the Office of Research and Development, Environmental Protection Agency. Work was completed as of December 31, 1975. iii ------- CONTENTS Page Abstract iii List of Figures vii List of Tables viii Acknowledgments xi Sections I Conclusions 1 II Recommendations 2 III Introduction 3 Volatile Compounds of Interest 3 Project Objectives 7 IV Identification of Airborne Volatiles From 8 a Swine Confinement Building Using Porous Polymers Background 9 Materials and Methods 11 Results and Discussion 15 Summary 22 V Effect of Ration Formulation on the 24 Evolution of Volatile Ammonia and Hydrogen Sulfide from Cattle Manures Supplement with,. Essential Oils 24 Ammonia Release and Olfactory Evaluation 27 as a Function of Feces, Urine and Water Ratios Effect of the Grain Source on the 32 Volatilization of Ammonia and Hydrogen Sulfide Relationship Between Grain Source and 36 pH of Animal Wastes v ------- CONTENTS (continued) Sections Pac Effects of Moisture on the Volatilization 37 of Ammonia and Amines Effect of Feces, Urine, Water and Storage 39 Period on Ammonia Release Effect of Various Animal Waste Character- 44 istics on the Evolution of Ammonia and Volatile Nitrogen Gases Summary 45 VI Ammonia Evolution Rate From Various Surfaces 50 Associated with Livestock Production Rate Measuring Device 50 Evolution Measurements in the Laboratory 56 Reedlot Odor Study 58 VII References 63 VIII List of Publications 69 VI ------- LIST OF FIGURES No. Page 1 Rating Form for Olfactory Evaluation of 29 Manure Odors 2 Apparatus for Trapping Evolved Ammonia 30 and Hydrogen Sulfide 3 Apparatus Used to Trap Evolved Ammonia 33 and Amines 4 Ammonia Evolution Rate for Urine, Feces, 43 and Combination as a Function of Time 5 Construction of the Sampling Box to 51 Capture the Released Volatile Compounds from a Soil Surface Previously Exposed to Animal Manures 6 Laboratory Apparatus Used to Evaluate the 57 Absorption of Odorants Using Contact with Water in a Counter Current Exchange Column 7 Laboratory Apparatus Used to Evaluate the 59 Ability of Various Absorbing Materials to Remove Ammonia from Odorous Air Vll ------- LIST OF TABLES No. 1 Volatiles Identified from the Swine Center Atmosphere Using the Trap Method and Combined GLC Mass Spectral Analysis 2 Compounds Detected by Selective Absorption 18 and GLC 3 Fixed Gases Found Over a Slurry of Manure 19 and Water. Gas Samples Injected Directly into Chromatograph with a Thermal Detector 4 Concentration of Volatiles in 500 1 of Swine 20 Center Air Passed Through Porapak Q Traps in 24 Hours 5 Basal Ration of Heifers During the Essential 25 Oil Supplementation Experiment 6 Summary of Data from the Olfactory Evaluation 27 of Manure Samples from Animals Fed Rations to Which Sagebrush and Peppermint Oil Had Been Added 7 Olfactory Evaluation and the Ammonia Release 31 Rate of Various Combinations of Feces, Urine, and Water 8 Correlations Between Water, Feces, Urine 32 Content and Rating, Ranking and Ammonia Release Rate for Manure Samples Incubated for 24 Hours at 30° C 9 Composition of Rations Fed Replacement 33 Heifers to Determine the Effect of Grain Source on Ammonia and Hydrogen Sulfide Generation 10 Effect of Grain Source and Level of Supple- 34 mentation on Hydrogen Sulfide Generation Rate by Mixture of 50 g of Feces and 50 g Urine from Replacement Holstein Heifers Fed Various Grain-Based Rations Vlll ------- LIST OF TABLES (continued) No. 11 Effect of Grain Source and Level of Supplementation on Ammonia Evolution Rate by Mixture of 50 g Feces and 50 g Urine from Replacement Holstein Heifers Fed Various Grain-Based Rations 12 Correlations Between pH and Ammonia 36 Evolution Rates for Corn, Barley, and Milo Rations 13 pH and Ammonia Evolution Rates from 37 Feces and Urine Mixtures from Corn, Barley, and Milo Rations 14 Correlations Between Mean Ammonia and 40 Amine Evolution Rates and Storage Period 15 Effects of Various Levels of Feces, Urine 41 and Water on Average Ammonia Evolution Rates 16 Correlations Between Average Ammonia 42 Evolution Rate and Length of Storage 17 Results of Fecal Matter Analyses for Ten 45 Heifers Fed Rations of 25, 50, and 75 Percent Barley 18 Ammonia and Total Volatile Nitrogen 46 Evolution Rates for Manure Samples from Ten Heifers Fed Rations of 25, 50, and 75 Percent Barley 19 Results of Urine Analyses for Ten 47 Heifers Fed Rations of 25, 50, and 75 Percent Barley 20 Correlations Between Ammonia Evolution 48 Rates and Urea, Crude Protein, Dry Matter, Total Volatile Nitrogen and Specific Gravity of Urine Samples and Between Urea Content and Specific Gravity of Urine IX ------- LIST OF TABLES (continued) No. Page 21 Evolution Rate of Ammonia from Several 52 Different Surfaces in the Vicinity of Livestock Production Facilities 22 Ammonia Evolution from Anaerobic Lagoon 54 Water Measured During the Summer of 1975 23 Ammonia Evolution from Anaerobic Lagoon 54 Water and Fresh Manure and Water When Additives Are Used 24 Absorption of Ammonia from Manure Gases 58 by Water in a Counter Current Exchange Column 25 Ammonia in Air After Passing Over Water, 60 Through Grass, Soil or Nothing 26 Ammonia in Air After Passing Over Water, 61 Grass, Soil, or Nothing ------- ACKNOWLEDGMENTS This project involved participation by the Departments of Animal Science, Microbiology and Agricultural Engineering at Oregon State University. The Animal Science Department participants were Dr. D. C. Church and Mr. R. 0. Kellems. From the Department of Microbiology were Dr. A. W. Anderson, Mr. M. D. Kelly and Mr. E. Mayes. The Agricultural Engineering Department participants were Dr. J. R. Miner, Mrs. Cheryl Gould, Mr. E. R. Hoffman, Mr. C. Henry and Mrs. C. I. Small. The commitment demonstrated by these persons and the numerous graduate and undergraduate students who assisted with par- ticular aspects of the research is gratefully acknowledged. Mr. R. Douglas Kreis, Project Officer, Office of Research and Monitoring, Ada, Oklahoma provided valuable assistance. This research was submitted in fulfillment of Grant No. S-802009 by Oregon State University under the sponsorship of the U.S. Environmental Protection Agency. Work was completed as of December 31, 1975. XI ------- SECTION I CONCLUSIONS The production, evolution, transport and perception of vola- tile compounds associated with livestock production involves a complex series of phenomena. Manure management has the potential for drastically modifying the overall process. Ration formulation, facility design, and specific treatment processes may also be used where appropriate to modify the system behavior to reduce volatile component production, alter the release process, modify the transport system, or, in certain instances, change the perception process. Solid absorbents developed for use in gas-liquid chromato- graphy have great capacity for absorption and retention of organic compounds. Although not fully perfected in this study, a sampling device fabricated of these materials has great potential for characterizing atmospheres containing manure-produced volatiles. Ammonia evolution from fresh beef cattle manure is largely from urine. The fecal contribution occurs only after significant anaerobic activity has become established. An essential oil added to the feed ration was carried in the urine and successfully altered the fresh manure odor by masking. The ammonia evolution rate sampling box designed in this project successfully met the need for a device to quantita- tively measure evolution rates of volatile compounds. It has been used to measure ammonia nitrogen release rates from a variety of surfaces. Due to the relationship which exists between ammonia release rate and odor production, the device is useful in evaluating odor control procedures which have previously been dependent upon qualitative judg- ments . ------- SECTION II RECOMMENDATIONS This project was designed to identify areas suitable for full exploitation in the control of volatile organic emissions from livestock production enterprises. It is recommended that those aspects of the project showing greatest potential be further developed. The use of solid absorbents fabricated to allow convenient exposure in an atmosphere of interest has potential as a quantitative measuring scheme. When perfected, such a system will allow inexpensive surveillance of suspected emission sources and allow definitive measurement of con- ditions in downwind areas. Mint oil was effective in masking the odor of fresh manure. Other lower cost essential oils should be sought as feed ingredients. The ammonia evolution rate measuring system perfected as part of this project has widespread application in measuring the evolution of ammonia from agricultural activities but may serve as a model for other measurement systems. It has immediate application in evaluating the effectiveness of feedlot odor control programs. ------- SECTION III INTRODUCTION Confinement livestock production schemes have been adopted for most species throughout the country. They have sufficient economic advantage over the more dispersed systems of the past to assure their continued importance in the overall food production complex. Water pollution attributable to runoff from livestock pro- duction areas and discharge of animal manures has been well documented and means for its control investigated. The discharge of potential pollutants into the air has been less well studied and control procedures are not in widespread use. Two effects of airborne pollutant release have been identified: odor complaints and transport of water pollutants via air movement to surface waters. This project was designed to open this area of concern and to quantify release rates for the most pertinent compound/ ammonia. VOLATILE COMPOUNDS OF INTEREST Ammonia The presence of ammonia as a component of our atmosphere was noted 100 years ago by Scholssing.1 Some of the physio- logical disorders specifically caused by ammonia were de- scribed by Weatherby2 with the primary effect noted on the lungs, eyes, and mucous membranes. Ammonia was found to reduce chicken resistance to Newcastle disease and in- crease air sac lesions in turkeys.3 It was shown by Charles and Payne1* that elevated levels of ammonia in chicken houses had an adverse effect on the growth of chickens. Boyd et al.5 studied the effect of ammonia gas poisoning on rabbits and cats. ------- The increased nitrogen concentration of surface waters in close proximity to livestock production units has generally been attributed to surface runoff from these units. The absorption of nitrogenous compounds directly from the at- mosphere by surface acid traps was found, however, to be 20 times greater for traps located in close proximity to a beef feedlot as compared to those some distance away.6 In more recent work (Luebs et al.7), the ammonia concentrated in air was measured and found to be increased 20-30 times in a concentrated dairying area as compared to nonagri- cultural areas. It was also noted that rainfall delivered three times the amount of ammonia inside a dairying area as outside. Ammonia has been demonstrated to be the primary nitrogen com- pound volatilized from feedlots.8 It has also been demon- strated that, under typical conditions, the ammonia will be present in quantities below its odor threshold.9 Miner and Hazen10 found this to be the case in swine building gases; they detected ammonia, but below its published threshold. Between 11 and 60 percent of the ammonia from sewage sludge applied to crop land was lost during the first one to two days.11 As much as 65 percent of the nitrogen added in the form of animal waste to an anaerobic swine lagoon was found to be volatilized.12 The nitrogen in excreted urine was studied by Stewart13 under simulated feedlot conditions; he found approximately 90 percent was converted to ammonia. The rate of ammonia release from a feedlot surface was increased when the surface was disturbed, such as would occur in manure mounding.14 When the moisture content of manure was increased from 60 to 90 percent and the tem- perature from 10° C to 25° C, an increase in the amount of nitrogen volatilization was noted, with losses approaching 50 percent of the nitrogen content of the samples.15 Diluted poultry manure has been shown to produce more ammonia, but the undiluted sample volatilized more ammonia.16 In a densely populated dairying area, a diurnal fluctuation in the atmospheric ammonia concentration was noted, with low concentrations in the afternoon and high concentrations at night. l 7 The pH of the medium has a direct effect upon the form in which the ammonia is found; under acidic conditions, it is in the nonvolatile (NHit + ) form and under basic conditions, in the volatile (NH3) form.18 A direct correlation between soil pH and ammonia volatilization was found when manure was mixed with different soil types.19 ------- Urea in urine has been indicated as the primary precursor of ammonia from animal wastes.13 It has been estimated that half of the nitrogen eliminated under normal con- ditions is in the form of urea.20 Ammonia was consis- tently identified in the gaseous exhaust products from anaerobically and aerobically stored dairy wastes.21 Amines The production of amines as by-products of decomposition of animal wastes has been proposed as a reaction between ammonia, an end product of protein and urea breakdown, and alcohols, products of carbohydrate degradation.22 The odor thresholds for the amines are very low, with trimethylamine having a threshold that is 100,000 times less than ammonia.23 Thus, a relatively small quantity of amines present as products of animal waste decomposition could play a major role in the odor intensity and offensiveness associated with livestock production units. Amines have been detected in the atmosphere associated with livestock confinement units. Trimethylamine was identified as the major amine present in the gases generated from cattle feedlots.9 This was supported by White et al.2 ** who also identified methylamine and ethylamine in gases associated with dairy animal wastes. Low concentrations of amines in swine manure have also been identified by Miner and Hazen.x ° Luebs et al.25 indicated that less than 5 percent of the volatilized nitrogen compounds absorbed from a large dairy area were not ammonia. The amine content of poultry manure was found to increase and the uric acid decreased with the length of storage.26 Hosier,27 using Chlorella ellipsoidea, a typical algae found in streams and lakes, studied the effect of amines volatilized from cattle feedyards on the growth of algae if absorbed by surface waters. Results indicated that growth was inhibited. ------- Hydrogen Sulfide The presence of hydrogen sulfide as one of the volatile gases generated from animal wastes has been reported by DaY §i al«28 an<3 Hammond et al.29 Hydrogen sulfide was found to be produced during the putrefaction process of swine manure; minimum concentrations for identifiable odor were 0.7 ppm. The assumption can be made that hydrogen sulfide is one of the gaseous products generated during the decomposition of animal wastes and that its precursors would be proteins and inorganic sulfur compounds. When swine were exposed to 8.5 ppm or 2 ppm of hydrogen sul- fide in combination with 50 ppm of ammonia under confinement conditions, it was shown that hydrogen sulfide had little effect on the rate of gain or feed efficiency.30 The description of the effects of hydrogen sulfide by Taiganides and White31 on poultry, swine, and cattle gives the symptoms associated with different levels and exposure periods. Chromatographic analyses of gases from accumulated liquid poultry manure by Burnett32 indicated that the odor-causing pollutants were identified as hydrogen sulfide, ammonia, diketones, mercaptans, sulfides, organic acids, indole and skatole. Merkel et al.2 2 performed odor evaluations, using selective absorbent solutions to alter the odor from swine wastes, and concluded that amines and sulfides were the major odor constituents. In bovine confinement operations, hydrogen sulfide has been found as a component of the volatile gas mixture generated during the process of waste decomposition. Stephens9 developed gas Chromatographic techniques for the analysis of cattle feedlot odors and identified amines, sulfur-containing compounds, and low molecular weight organic acids in the gases. White et al. 2 ** found that similar effects with dairy animal waste indicated the presence of sulfides, disulfides and the esters of organic acids. Bethea and Narayan33 detected hydrogen sulfide as the only sulfur-containing compound when beef cattle wastes were maintained under aerobic conditions by bubbling air through the samples. In studies with swine, the production of hydrogen sulfide was found to be highly correlated with temperature, ratio of pit area to building volume, air retention time of the building, and daily sulfur intake of the animal. 31f ------- PROJECT OBJECTIVES The first objective of this project was the preparation of a comprehensive state-of-the-art review concerning livestock waste odors. This material was compiled and a 125-page re- port based upon the work published in 1974. That publi- cation continues to be of interest and requests are fre- quently received. The effect of cattle ration on ammonia and hydrogen sulfide release from manure under various treatment schemes was investigated. Those results are included in this report. A simple technique for identifying and measuring odorous compounds released from decomposing animal manures was sought. Solid absorbents were utilized in a variety of physical configurations. The successes and difficulties involved in this approach are recounted in Section IV. A technique was needed to quantitatively measure the evolu- tion of pertinent volatile compounds from specific surfaces associated with livestock production. A sampling box was de- signed and constructed to facilitate these measurements, which are summarized in this report. ------- SECTION IV IDENTIFICATION OF AIRBORNE VOLATILES FROM A SWINE CONFINEMENT BUILDING USING POROUS POLYMERS Odors associated with livestock production are generally related to manure; however, other odors from the animals themselves, dead animals, feed, or cleaning compounds and medicines may also contribute to the total atmospheric load. Manure is a mixture of carbohydrates, fats, proteins, and their products and, as such, is a natural growth sub- strate for microorganisms. When manure undergoes decom- position as a result of microbial growth, volatile metabolic end products and their intermediates escape into the atmo- sphere. This is a prime source of odorous gases. The main products in carbohydrate decomposition are acids, aldehydes, alcohols, ketones, carbon dioxide, methane, and water. Lipids are degraded into fatty acids and glycerol; the fatty acids break down into acetyl CoA, plus numerous smaller chained fatty acids, by beta-oxidation. Proteins are hydrolyzed, cleaving the large molecules into amino acids. The amino acid decomposition can proceed in many ways depending on the organisms present and the environment. General reactions of amino acids include trans- emination, decarboxylation, racemization, and deamination. Many end products and intermediates are possible from amino acid decomposition including ammonia, hydrogen sulfide, acids, amines, mercaptans, sulfides, alcohols, aldehydes, ketones, esters, and alkyl ring structures. ------- The decomposition of manure is a stepwise process in which complex organic compounds are degraded into smaller mole- cules. Any combination of these is possible, and the observed odor represents the sum of the individual con- stituents. Research to identify the chemical compounds present has yielded about 45 compounds.18 This list is undoubtedly incomplete, but does indicate the complexity of the problem. Until recently, the measurement of volatile gases at ex- tremely low concentration levels by the usual analytical methods has not been possible. However, recent developments in gas chromatography, mass spectroraetry and methods of concentration and trapping have enabled researchers to sepa- rate and identify volatile compounds with relative ease. BACKGROUND Direct sampling was used at Cornell University by Burnett and Sobel3 for identifying odors from poultry manure. The manure was filtered and centrifuged and the supernatant injected directly into gas chromatographs. The low con- centration of compounds and the differences in concentra- tions of components from the liquid waste and the air make this method undesirable. Merkel36 used a salting-out technique to identify volatiles from swine manure. Anhydrous inorganic salts are added to a sample solution. The mixture is then shaken and heated to 60° C to release the dissolved gases. A sample of the headspace gas is then injected into the chromatograph. This method is easily and quickly conducted. Heating, however, may alter the normal conditions of the waste and the efficiency of the salting-out effect is undefined. Selective absorption techniques involve contacting gases with specific reagents in which they are either soluble or form stable nonvolatile products. This concentration method was used to isolate alcohols, amines, carbonyls, and sulfur derivatives by Merkel et al.2 2 Nitrogen was bubbled through a liquid manure sample and through a series of tubes contain- ing the selected absorbents. The absorbed compounds were regenerated by various means and the expelled gases or distilled liquids were injected into the chromatograph. Some of the procedures are tedious and time consuming and may not be representative of those odors characteristic of the barn atmosphere. ------- Frus et al.3 7 used a flask containing potassium dichromate- sulfuric acid solution to trap gases from a sample of manure. The gases from the manure were bubbled through the solution for chemical oxygen demand (COD) analysis. The COD technique was sensitive to individual organic gases believed to contribute to manure odor, but whether air COD is an overall measure of the level of organic gases is unknown. Atmospheric ammonia has been measured by absorption in dilute acid. Ammonia absorption rates measured near feed- lots were as much as 20 times greater than controls.6 Ammonia was measured in a swine building atmosphere by absorbing in a 2% boric acid solution and then using Nessler's reagent to form a typical color whose intensity can be measured at a wavelength of 420 my.10 Absorption techniques- have been tried in the detection of amines in the air from an animal chamber bubbled through 5% acetic acid. After 12-48 hours of aeration the liquid was subjected to chromatographic analysis.11 Several amines were detected; however, the chromatographic identifications were questionable and results were not verified by an alternate method. The dilute acid trap technique has also been used to absorb basic compounds volatilized from cattle feedlots. The collected trappings were returned to the laboratory, filtered and evaporated to dryness at 50° C under vacuum. The resultant residue was taken up on a few milliliters of the dilute acid and analyzed for amines by gas chromatography.38 Ten different amines were identified by this procedure. The biggest drawback to direct sampling, salting-out and some selective absorption techniques is that the compounds identified may not be physiologically responsible for the odors detected by the nose, or for those which occur naturally in the vicinity of the barnyard, especially if samples are taken under laboratory conditions. These dilute acid traps at the feedlots and subsequent chromatographic analyses may not be detecting the same compounds as the nose. Further tests are needed to substantiate this. Vapors can be condensed at various temperatures. This method was used in identifying the volatile components of skim milk.39 The condensate from various traps may be injected into the chromatograph. However, transfer of the condensate requires special handling methods and has been little used. 10 ------- Air can also be sampled by circulation through, cold traps in dry ice or liquid gas;36'1*0 however, this method is trouble- some unless the moisture has been removed. Desiccants may be used to remove moisture, but they often absorb odor as well. The optimum system depends on the selection of an appropriate cryogen. For this purpose liquid oxygen has been found to be the best since it does not liquefy the major component of air and efficiently freezes out low molecular weight compounds. ** ° Dry ice is readily available and the easiest to work with but does not retain hydrogen sulfide efficiently. Cryogenics may prove to be the most efficient method for collecting volatiles, though not the simplest. Zlatkis e_t al. **1 adsorbed headspace gas of volatile organic metabolites in human urine by heating, then letting the vapors pass through a short water condenser, and finally onto a porous polymer trap. The trap was then inserted into a modified injector port of a gas chromatograph. Fifty-one compounds were identified by this method. Miller1*2 identified methyl mercaptan, dimethyl disulfide, dimethyl trisulfide, 3 methyl-1-butanol, and a trimethylamine produced in fish muscle by certain bacteria. The volatiles were collected on Porapak Q traps for subsequent condensation in a capillary column and then volatilized for gas chroma- tographic-mass spectral analysis. Porapak Q was also used to entrain any organic volatiles emitted from female fir beetles as a sexual attractant.^3 A combination of selective absorption and headspace trapping was used by Hartung et al. **lf to identify carbonyl compounds in a swine building. Sample air was pulled through a column packed with silica gel impregnated with aqueous acidic DNPH solution. Carbonyl compounds in the air samples were con- verted to DNPHs (2,4-dinitrophenylhydrazones) and eluted from the column with hexane. The elute from the reaction column was evaporated to a small volume and spotted on thin layer chromatography plates. MATERIALS AND METHODS Air samples were taken from inside the Oregon State University swine barn from a platform 2.5 m above the floor. The 150-175 swine in the barn were being fed a corn-based ration through the sampling period. The partially slotted floor building was washed completely once a week with 11 ------- manure, wash water, and liquid manure from the under-floor storage pit going into an anaerobic lagoon about 50 m from the confinement area. The water from this pond is pumped out and used for crop irrigation. Initial Traps Volatile compounds were trapped on Porapak Q (80/100 mesh ethylvinylbenzenedivinylbenzene polymers) and Tenax GC (35/60 mesh 2,6-diphenyl p-phenylene oxide polymers) packed inside stainless steel traps 103 mm by 6 mm outside diameter (O.D.) by 3 mm inside diameter (I.D.). Air to be sampled was drawn through a glass manifold holding four traps for 24 hours using a small Dyna-Vac pump. The traps could then be run immediately or stored in refrigeration without any loss of volatiles. All sample traps were purged with nitrogen (30 ml/min) for one and a half hours. The traps were first heated to 55-60° C for one hour to remove traces of water and then reversed and reheated to remove the trapped vola- tiles. The traps were first heated to remove excess water because water interferes with the spectrum and is harmful to the ionizing tube in the mass spectrometer. Excessive water in the gas chromatograph has a tendency to broaden the peaks and run them together. The Porapak Q traps were then heated to 150-160° C for thirty minutes, while being purged with nitrogen, to transfer the entrained volatiles to an open tubular stainless steel trap 150 mm by 1.25 mm I.D. immersed in dry ice. The Tenax traps were heated to 200° C. The small cold traps were connected to the gas chromatograph by a modified inlet system. The cold traps were transferred to the mass spectrometer in dry ice and connected by a modified inlet system. In both instances the cold traps were heated with a heat gun that reaches 500° C to volatilize the entrained odor constituents. Over 30 Swine Center samples were studied using the initial sampling traps. The technique involved a 24-hour sampling period and about four hours of sampling preparation and gas- liquid chromatography (GLC) separation. By using multiple traps several samples were simultaneously taken and/or stored for later analysis. The traps were purged for 24 hours with helium or nitrogen at 200° C before re-use. Cold traps were checked in the lab for odor retention before being run on the chromatograph. After purging 103 mm traps loaded from both the Swine Barn and OSU campus into the open tubular stainless steel traps in dry ice, the cold traps were removed from the dry ice and heated to let the trapped volatiles escape into the atmosphere. The escaping volatiles were then smelled by several people in the lab to obtain a relative comparison of the two odors. 12 ------- Revised Traps In order to overcome the difficulties inherent in long packed columns as a volatile gas collection device, an al- ternate trap was devised. The new traps were constructed from 150 mesh stainless steel screen and silver soldered into 180 mm x 6 mm tubes. A small wire hook was soldered to one end. These tubes were cleaned with a brush and pipe cleaner inside and out with hot water, dried in an oven at 176° C for one-half hour, rinsed with dimethylchlorosilane and anhydrous methanol, and dried in an oven again at 176° C overnight. With proper cleaning, conditioning, and handling (no grease or direct contact with chemicals or sewage) tubes do not need this rigorous cleaning again. Dust is shaken or blown off with clean filtered air. Using clean gloves or forceps to prevent contamination, the fabricated tubes were packed with 0.85 ± 0.05 grams of a 50:50 mix by volume of Tenax GC (60/80 mesh 2,6 diphenyl- p-phenylene oxide polymers) and Porapak Q (ethylvinylbenzene- divinyl benzene polymers) held in place with silane treated glass wool. Tubes thus filled are placed in pyrex sample tubes and plugged with teflon cylindrical septums. Filled traps were placed in sample tubes and conditioned for 24 hours at 200° C in a co-distiller tube oven with a flow of purified nitrogen (02 and H20 removed) at 30 ml/min. Conditioned traps sealed in glass sample tubes under purified nitrogen were transferred to the sampling site. Traps in glass tubes are either connected directly to manifold or vacuum pump for flow through sampling or are withdrawn from tubes with a wire hook and then placed on hoods inside plastic dust and water protective containers with clean gloves or forceps. A flow rate of 310 ml/min/trap (930 ml/min for a manifold holding three traps) was preset and checked at the site with a flow meter. Sample periods used were from 1 to 24 hours (18.6 to 446 liters of air) for pumped-in sampling. After sampling, traps were transferred to the laboratory in the plugged glass sample tubes. Samples can be stored in sample tubes in a refrigerator at -5° C for several days without volatilization loss or noticeable contamination. Loaded traps were purged with helium at a flow rate of not more than 20 ml/min at a temperature of 150° C for 2 hours. If samples were to be analyzed by mass spectrograph, the small amounts of water present in the traps were removed by first purging the traps with purified nitrogen at 50° C for 1 hour. Volatiles were 13 ------- collected in a 1-meter long 0.16-cm I.D. stainless steel capillary tube which had luer-lok syringe devices silver soldered to each end. This appartus was immersed in liquid nitrogen at -196° C and purged with helium. The outlets were equipped with miniert teflon shut-off valves with luer-lok attachment. When samples were collected, the valves were shut and plastic disposable 10-ml syringes filled with 8 ml of purified helium were attached to the inlets of four traps C3 for sample replicates and 1 for reference control). With syringes attached and valves shut, the traps were gas tight and could be pressurized for direct injection. Pressurized direct injection on column was found to be the most efficient and gave the best resolution. Two chroma- tographic columns were used, one for amine separation and one for aliphatic acids separation. Dual column-detector set-up and settings were used for all analyses to remove column bleed or ghost peaks coming from the packings and stationary phases used at high temperatures. Chromatography The analyses were made on an F & M Model 402 gas chroma- tograph fitted with a dual flame ionization detector (FID), a Honeywell strip chart recorder, and a Hewlett-Packard 3370A integrator. A Beckman GC2A with a thermal detector was used to identify fixed gases. A Finnigan 1015C mass spectrometer in conjunction with a Varian Aerograph series 1440 GLC was used for mass spectral analysis. The following chromatographic columns were used: a 1.83 m x 3.18 mm O.D. stainless steel tubing packed with a 5% Triton X305 coated on 100/120 mesh Chromosorb W; a 1.83 m x 3.18 mm O.D. stainless steel tube packed with 4% Carbowax 20 M + 0.8% KOH on Carbopack B; a capillary column 30.5 m x 0.75 ram I.D. stainless steel coated with 5% Ethylene Glycol Succinate (EGS); a 61 m x 0.75 mm I.D. capillary stainless steel column coated with 5% Triton X305; and a 153.8 m by 0.75 m I.D. capillary stainless steel column coated with 8% Carbowax 20M. Carrier gas flow rates were: 30 ml/min of helium for the 3.18 mm columns and 12-15 ml/min of helium for the capillary columns. The columns used with the thermal detector were run iso- thermally at 40° C. The Carbopack B column was run iso- thermally at 90° C. The Carbowax capillary column was oper- ated at 70° C for five minutes and then temperature programmed 14 ------- to 150° C at 2° C/min. The Triton X305 capillary column was programmed to operate at 60° C for five minutes and raised to 150° C at 4° C/min and held. The EGS column was pro- grammed to run at 110° C for four minutes and raised to 175° C at 4° C/min and held. The 3.18-mm Porapak Q and Triton X305 columns were used with the thermal detector for free gas identification. The Triton X305 and Carbowax 20M capillary columns were used for general identification, the EGS column was used for free acids and the Carbopack B column was used for amines with the FID system. Selective absorption was used to identify alcohols and carbonyls. Nitrogen was bubbled through a manure slurry in a three-liter flask and then into a collecting tube contain- ing 25 ml of propylene glycol for absorbing alcohols. Any carbonyls absorbed were removed in carbon tetrachloride by successive steps of liquid extraction using the technique described by Suffis and Dean.45 The solutions were dis- tilled and injected into the gas chromatographs. RESULTS AND DISCUSSION Initial Traps Table 1 shows the compounds identified, the traps and columns used, and the compounds' retention times. Many of the compounds were detected from more than one column, but for convenience, only listed once. There were two xylene isomers and several alkyl benzene isomers seen, hence the variation in retention times. This is in agreement with recent work done by Hammond e_t al. ^6 using a similar trapping method with Chromosorb 102 as the collecting agent. The major organic constituents they collected were a series of alkylated aromatic hydrocarbons. Junk and Svec"7 also found many alkylated aromatic compounds plus the aliphatic acids hexanal and diacetal in air, using macroreticular resins as trapping materials. Table 2 shows the compounds detected by selective absorption. The alcohols of greatest concentration were ethane i and butanol. 15 ------- Table 1. VOLATILES IDENTIFIED FROM THE SWINE CENTER ATMOSPHERE USING THE TRAP METHOD AND COMBINED GLC MASS SPECTRAL ANALYSIS Compound 2 butanol Sec-butanol Hexanal Dimethyl disulfide (DMDS) 3 amino pyridine n-butanol Dimethyl trisulfide (DMTS) Toluene Xylenes Alkyl benzenes 2 , 3 butanediol Ace to in Indane Benz aldehyde Me-naphthalene Diacetyl 2-octanone Acetic acid Propionic acid N-butyric acid Columna T T T T T T T T T T T T T T T C C E E E Trap T,P T,P T,P T,P T T,P T T,P T,P T,P T,P T,P T T,P T T,P T T,P T,P T,P Retention time, seconds 75 81 97.5 105 120 140 450 130 variable variable 170 180 345 540 1440 240 210 85 115 *m mm -» 150 ------- Table 1 (continued). VOLATILES IDENTIFIED FROM THE SWINE CENTER ATMOSPHERE USING THE TRAP METHOD AND COMBINED GLC MASS SPECTRAL ANALYSIS Compound Valeric acid Acetophenone Caproic acid Enanthic acid Phenol P-cresol 2-ethoxy-l-propanol Et-phenol Benzoic acid Trimethyl amine (TMA) Column3 E E E E E E E E E B Trap T,P T T T,P T,P T,P P P P T,P Retention time, seconds 210 240 275 300 455 515 195 580 645 75 Column packings were: T - 5% Triton X305 on 100/120 mesh Chromosorb W C - 4% Carbowax 20M plus 0.8% KOH on Carbopack B E - 5% Ethylene glycol succinate on a stainless steel capillary column B - 8% Carbowax 20M on a stainless steel capillary column 'Trap packings were: T - Tenax GC P - Porapak Q ------- Table 2. COMPOUNDS DETECTED BY SELECTIVE ABSORPTION AND GLC Compound Column Absorbent Methanol Triton Propylene glycol Ethanol " " N-propanol " " Iso-propanol " " N-butanol " " Iso-butanol " Formaldehyde Carbowax Carbon Tetrachloride Acetaldehyde " " Propionaldehyde " " Iso-butyraldehyde " " Heptaldehyde " " Valeraldehyde " " Octaldehyde " " Decaldehyde " " Table 3 shows the fixed gases found over a slurry of manure and water. Samples were taken in a gas tight syringe and injected directly into a column of a gas chromatograph equipped with a thermal detector. The Triton X305 column was used for sulfides and the Porapak Q column for methane, carbon dioxide, nitrous oxide, and nitrogen. No satis- factory column was found for the identification of ammonia; consequently, the Nessler's chemical test was used to confirm its presence. Carbon dioxide and methane were the most abundant gases found. Traps were also set up outside Nash Hall on the OSU campus about one and a half miles from the Swine Center. Compounds identified on the Triton X305 column were very similar between the swine barn and the OSU campus. The alkyl benzene isomers were common to both locations, the only difference being that the concentrations were slightly higher from the Swine Center. However, the chromatographic results on the EGS column in similar locations were very different. The acid and phenolic compounds were absent from traps exposed on campus. The chromatographic results from the Carbopack B column for amines were surprising. 18 ------- Table 3. FIXED GASES FOUND OVER A SLURRY OF MANURE AND WATER. GAS SAMPLES INJECTED DIRECTLY INTO CHROMA- TOGRAPH WITH A THERMAL DETECTOR Gas Column Relative Retention Time N2 CHij CO 2 H2S NH3 Porapak " " Triton Chemical absorption 30 36 85 70 seconds seconds seconds seconds The campus chromatograph showed more peaks than the one of the Swine Center. Trimethylamine was the only compound positively identified and was most prominent in the Swine Center. Isopropyl amine was tentatively identified in both places. Dimethylamine was tentatively identified from the Swine Center and ethylamine from the campus sample. By using a gas chromatograph equipped with an integrator, a quantitative check could be made on various compounds. One microliter of standard solution was injected into the gas chromatograph giving concentration readings in millivolts. By using the formula: 1 yl of known = 3500 x 103 mvolts (standard value) X yl of unknown = integrator presentation in mvolts X (3500 x 103) = (1 yl) (integrator presentation of unknown) The amount of unknown was determined in microliters and was converted to micrograms. Approximately 720 liters of air passed through each Tenax trap and 500 liters through each Porapak Q trap in 24 hours; the fraction of unknown volatiles is given in yg/1 (Table 4). Two traps were set up in a series to see if any acids were being missed. The chromato- gram from the second trap was either negative or too small to measure for the acids. It was, however, found that not all of the aromatic hydrocarbons were retained on one trap alone. The values determined for acids by this method were well below threshold limit values.18 19 ------- Table 4. CONCENTRATION OF VOLATILES IN 500 1 OF SWINE CENTER AIR PASSED THROUGH PORAPAK Q TRAPS IN 24 HOURS Compound Date Recorder Presentation in Millivolts yg x 10 -4 jjg/1 x 10" Acetic it ii ii Propionic ii H H Butyric ii ii H Valeric H it ii Phenol ii ii M Cresol ii H ii DMDS ii Xylene n 5/03/74 5/10/74 5/17/74 5/24/74 5/03/74 5/10/74 5/17/74 5/24/74 5/03/74 5/10/74 5/17/74 5/24/74 5/03/74 5/10/74 5/17/74 5/24/74 5/03/74 5/10/74 5/17/74 5/24/74 5/03/74 5/10/74 5/17/74 5/24/74 5/17/74 5/24/74 5/17/74 5/24/74 1140 1333 3996 3990 910 500 8738 8610 1065 800 286 5660 2663 3863 485 1700 2942 5667 1910 5660 3580 8863 7878 8610 5040 2663 6995 8738 3.42 4.0 12.0 12.0 2.6 1.43 25.0 23.0 2.92 2.2 0.79 17.3 7.17 10.4 1.32 4.6 9.0 17.4 5.46 17.3 10.6 26.0 23.4 23.0 15.2 7.17 17.6 25.0 6.84 8.0 24.0 24.0 5.2 2.86 50.0 46.0 5.84 4.4 1.58 34.6 14.34 20.8 2.64 9.2 18.0 34.8 10.93 34.6 21.2 52.0 46.8 46.0 30.4 14.34 35.2 50.0 20 ------- Revised Traps Problems previously encountered in multiple sampling handling of several traps simultaneously, reproducibility, resolution, and efficiency of gas chromatographic analysis have been reduced or eliminated. With a larger quantity of adsorbent in each trap, a greater number of volatiles are adsorbed in a shorter time period and theoretically reduce the possibility of selectivity. The new holder for the adsorbent (made from stainless steel, 150-mesh screen silver soldered into a tube with wire hook at one end and plugged with silane treated glass wool) promises to be a simple way to trap air pollutants. When the traps were placed in volatile contaminated atmospheres, they trapped as many or more volatiles by adsorption than by forced pumping of air through them. Changing the method of sample injection from indirect diversion through a sample loop to direct pressurized in- jection avoided disruption of carrier gas flow through the column, which gives an off-scale deflection on chart for up to 30 seconds while restabilization of instrument and column flow takes place. The pressurization of sample gives better resolution due to the recommended fast plug injection rather than the slower diffused injection from sample loops. The modified cold traps are used as syringes after warming with a heat gun to revolatilize the collected samples. The units are sealed at the outlets with miniert valves after collection. Then 10-ml plastic disposable syringes filled with 2-8 ml of helium are connected to the inlets via luer-loks. The plastic components of the system appear not to have introduced any plasticizer contaminants in high enough levels to be of any significance, as all properly conditioned blank traps run under the same conditions and sensitivities on the gas chromatograph showed only traces of air and water. The short chain aliphatic primary amines (methyl, dimethyl, ethyl, isopropyl, and trimethyl) have been tentatively identified in animal house air as well as in countryside odor-free air by comparison with known amines, using a column specific for amine separation. None of the individual amines could be clearly identified as unique to individual types of animal house odors monitored (swine, dairy, and poultry). All reference controls of samples taken in odor- free air seven miles from the city limits of Corvallis, Oregon, and about eight miles from any animal feedlots show 21 ------- identical peak patterns and comparable quantities of volatile material. Blank traps have always shown clean traces, so it appears that the odorous compounds are not being collected in sufficient amounts or are masked by the larger amounts of other organic compounds present in so-called "clean odor-free SUMMARY The main difference between the air of the Swine Center and OSU campus was the dimethyl disulfide (DMDS), the mixed acids, and the trimethylamine (TMA). All would result in a marked odor. DMDS and TMA have a putrid smell and the acids are pungent. The major organic constituents collected at both locations are alkylated aromatic hydrocarbons. Most hydrocarbons have a relatively high odor threshold and do not leave odors characteristic of swine rearing facilities. Exceptions are the naphthalene compounds, which have a mothball odor, and the cresols, which have a preservative smell. Many of the compounds identified are well known flavor constituents in food such as diacetyl, butyric acid, and p-cresol, which occur in dairy products, and hexanal, a common constituent of vegetables and their fats.1*8 Both organic absorbents used, Porapak Q and Tenax, selec- tively retain those compounds having at least two-carbon atoms and are useful as adsorbents for volatile organic compounds. Most one-carbon compounds probably are not retained or may be lost during the water purge. Miller et al. , **2 however, did identify methyl mercaptan, a one-carbon compound produced from fish muscle by a bacteria, using a Porapak Q trap following a water purge of one hour at 55° C. Another method may be required in order to effi- ciently trap one-carbon compounds. The large number and complexity of compounds of potential importance in odorous air account for the difficulty en- countered in odor analysis. It also helps explain the variability in the detected odors commonly found in wastes. The objection to manure odors arises from the particular concentration and combination of volatiles present. The compounds found in the Swine Center were each individually below danger threshold for man; however, this does not mean that they are not an odor nuisance. Air in other confine- ments in which wastes are handled differently may have different odorous constituents. 22 ------- The work with, the modified traps was designed to find a simple means of using gas sampling and analysis of complex mixtures by gas chromatography to discover unique odorous indicator compounds which might allow quantitative and routine monitoring of odorous air associated with concen- trations of animals. A major problem encountered was inter- ference from other relatively nonodorous organic volatiles (carbonyls, alcohols, and aromatics) present in larger concentrations which must be removed for clear routine monitoring of the odorous volatiles. A method to selectively adsorb or desorb volatiles on traps is needed. Mixtures sometimes showing compounds that had retention times identical to amines or acids could not be confirmed by mass spectral analysis. Quantitation of individual compounds (peaks on the chromatogram) could not be made without reservation. Total amounts of volatiles trapped were quantified and resulted in concentrations 2-3 magnitudes below perceptible concentrations of highly volatile and odorous compounds (trimethylamine-14.0 x 10~2 yg/1 and ethyl seleno mereaptan-18.0 x 10" ^ yg/1 vs. highest total volatile concentration measured at 37.0 x 10-5 ml/1). Quantities were calculated using an internal standard of known quantity (1 yl amine mixture and 1 x 10~3 yl acid mixture). Variations in temperature, humidity, wind velocity, and number and activity of animals from hour to hour make it difficult to correlate odor intensity with volatile profile and quantity. Since exchanges can occur on the adsorbent, short trapping periods are probably best. No patterns could be seen in longer exposures. Many times it was noted that the quantity of volatiles trapped would decrease after extended exposure. 23 ------- SECTION V EFFECT OF RATION FORMULATION ON THE EVOLUTION OF VOLATILE AMMONIA AND HYDROGEN SULFIDE FROM CATTLE MANURE The nuisance complaints associated with animal production units are frequently due to odors. Considerable research effort has been directed toward developing waste management techniques and procedures for handling wastes after they have been produced. Only limited research has been directed toward modifying rations to control the odors associated with the subsequent wastes. SUPPLEMENT WITH ESSENTIAL OILS Background Supplementing swine rations with Lactobacillus acidophilus, yeast activated charcoal, and sagebrush (5%) was shown to have no significant effect upon the olfactory evaluation of the wastes produced.lf9 50 Research conducted at Colorado State University indicated that a beef feedlot ration supple- mented with sagebrush at a rate of 0.5 to 1 kg/day-animal (1 to 2 Ibs/day-animal) was effective in reducing feedlot odors.51 Methods An experiment was designed to evaluate the effect of sup- plementing the rations of replacement heifers with two es- sential oils to determine their effects on the odors of the animal wastes. The materials tested were sagebrush and peppermint oil. Three separate olfactory evaluations were conducted using a group of five Holstein replacement heifers. The heifers were maintained on a basal ration of barley and alfalfa hay mixed to form a complete ration (Table 5) to which two levels (1% and 1.5%) of ground mountain big sagebrush (Artemisia 24 ------- Table 5. BASAL RATION OF HEIFERS DURING THE ESSENTIAL OIL SUPPLEMENTATION EXPERIMENT Ingredient Proportion Barley 0.250 Chopped alfalfa 0.696 Cane molasses 0,050 Cottonseed meal 0.004 tridentata ssp. vaseyana form xericensis) and one level (0.25%)of peppermint oil were added. A control group of five replacement heifers was maintained on the basal ration during the experimental period. All rations were fed ad libitum with free access to trace mineralized salt and water. Sagebrush was collected approximately 15 miles northeast of Bend, Oregon, in June of 1974. It was allowed to air dry to a moisture content of approximately 11%. The leaf portion was then ground in a Wiley mill equipped with a 1-mm screen. The ground sagebrush was frozen until the day it was added to the ration to reduce the loss of essential oils. Peppermint oil was obtained from a mint grower located in the Willamette Valley. A gas-liquid chromatographic analysis of the peppermint oil indicated it to be: 49.6% menthol, 22.5% menthone, 6.6% menthyl acetate, 2.5% menthofuran, and a number of other components in lesser concentrations. Urine and fecal samples were collected from the control and the supplemented groups on an individual animal basis. Fresh urine samples were collected from each animal by manually stimulating it to urinate, at which time approxi- mately a 200-ml sample was collected. Fecal samples were collected at the same time by removing a sample directly from the rectum of each animal. These samples were then returned to the laboratory where a composite sample was made for both the urine and feces from each group. 25 ------- Samples containing 50 g of feces and 50 g of urine from the composite samples were mixed in 300-ml Erlenmeyer flasks and incubated at 30° C for 24 hours prior to evaluation by an olfactory panel. The samples were removed from the water bath, dried, wrapped in paper, and allowed to stand at am- bient temperature for approximately 30 minutes prior to evaluation. The size of the olfactory panel varied from 13 to 30 members for each of the duplicate evaluations of the various treatments. The samples were evaluated using a trianglar testing pro- cedure in which two of the samples were duplicated; this procedure is similar to the olfactory evaluation methods reported by Amerine.52'53'5k The rating scale ranged from 0 to 15, with 15 the most offensive and 0 the least offensive. Samples were also ranked by offensiveness with the value of 1 given to the most offensive and 3 to the least offensive. Results and Discussion Comparisons were only made between samples that were evalu- ated by an individual panelist at one given time. The means and standard error of the means were calculated for the rating and ranking values that were determined in this manner and are given in Table 6. Addition of sagebrush to the ration at the 1% and 1.5% levels had no detectable effect upon (P > .10) the subsequent ol- factory evaluation of the manure. The peppermint supplemented ration was evaluated with and without the urine fraction, with an equal amount of distilled water replacing the urine. The samples containing both fecal and urine fractions were found to be less offensive (P < .05) than the basal plus urine. When the fecal waste from the peppermint supplemented animals was combined with distilled water and compared to the basal plus urine, a reduction in offensiveness was not observed (P > .05). This indicates that the urine fraction was responsible for the change in the offensiveness associated with the waste pro- duced when peppermint was added to the ration. A charac- teristic menthol odor was noted to be present in the urine obtained from the peppermint supplemented animals. It apparently partially masked the normal odor of urine. 26 ------- Table 6. SUMMARY OF DATA FROM THE OLFACTORY EVALUATION OF MANURE SAMPLES FROM ANIMALS FED RATIONS TO WHICH SAGEBRUSH AND PEPPERMINT OIL HAD BEEN ADDED Std Error Std Error Ration Rating Mean Ranking Mean 1% Sagebrush Sagebrush 1% 7.87a 1.008 2.13a 0.192 Basal 7.87a 1.241 1.93a 0.228 Basal 8.67a 1.058 1.67a 0.188 1.5% Sagebrush Basal 6.62a 0.605 2.07a 0.239 Sagebrush 1.5% 7.46a 1.163 1.77a 0.231 Sagebrush 1.5% 7.15a 0.799 1.461a 0.215 0.25% Peppermint feces only Peppermint 0.25% Peppermint 0.25% Basal 0.25% Peppermint Peppermint 0.25% Basal Basal 8-5a 6.9J 7.4a 6.00a 10.65° 9.68° 1.108 1.005 1.284 0.697 0.702 0.920 1.6* 2.2a 2.0a 2.65a 0.50b 0.221 0.30 0.30 0.170 0.151 0.158 a/ Means in each column with different superscript letters are significantly different (P < .05). AMMONIA RELEASE AND OLFACTORY EVALUATION AS A FUNCTION OF FECES, URINE AND WATER RATIOS Methods Feces and urine samples were collected from each of five Holstein replacement heifers being fed a ration of barley and alfalfa hay. The composition of the ration is given in Table 5. 27 ------- The procedure for urine and feces collection is the same as outlined in the previous trial. The collected urine and feces were then returned to the laboratory and the following samples were prepared immediately from a composite sample of urine and feces: 100 g urine; 50 g feces + 50 g water; 50 g feces + 50 g urine; and 25 g feces + 75 g water. Similar samples were prepared for each of the subsequent evaluations. The samples were allowed to incubate in a 30° C water bath for 24 hours prior to evaluation by an olfactory panel and presented to the olfactory panel for evaluation as described earlier. The rating was based on a scale of 0 to 15, with 15 the most offensive and 0 the least offensive. An example of the judging form used is shown in Figure 1. Panels ranged in size from 19 to 29 members. Rates of ammonia release for each of the various samples were determined just prior to presentation to the olfactory panel for evaluation. The trapping apparatus used is shown in Figure 2. A series of two dilute HCl (1:15 dilution with water) traps were used to trap the evolving ammonia. The head space gases were replaced at the rate of 0.5 1/min and ammonia quantities determined using the Nesslerization method.55 The results of the olfactory rating and ranking evaluations were correlated with the ammonia release rates to determine the relationship between these measurements. Results and Discussion The initial numerical rating and ranking values for re- lative offensiveness were not found to be noticeably dif- ferent (P > .10) for the samples evaluated (Table 7). This would indicate that the relative portions of feces, urine, and water of the samples have little effect upon the initial release of odorous compounds. The correlation coefficients for the various interactions are given in Table 8. The numerical ratings were not found to be correlated (P > .10) with the fecal, urine, or water content of the samples. The rankings of the samples were not correlated (P > .10) with the water content. However, a negative correlation (P < .05) for the fecal content and a positive correlation (P < .05) for the urine with respect to rankina was observed. 28 ------- Rating Scale m 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 L Sample Numbers Name Date Most objectionable Least objectionable Figure 1. Rating form for olfactory evaluation of manure odors 29 ------- 00 o BORIC ACID OR CADMIUM HYDROXIDE WATER BATH CADMIUM HCI (DILUTE) HYDROXIDE SOLUTION AIR SOURCE Figure 2. Apparatus for trapping evolved ammonia and hydrogen sulfide. ------- Table 7. OLFACTORY EVALUATION AND THE AMMONIA RELEASE RATE OF VARIOUS COMBINATIONS OF FECES, URINE, AND WATER Item 1.0 urine 0.5 0.5 Sample f eces 0 . 5 urine 0 . 5 feces water 0.25 feces 0.75 water Of fensiveness Mean Std. Mean Std. rating1' 2 error ranking l i 3 error 5. 0. 2. 0. 21a 48 47a 21 3. 0. 1. 0. 95a 51 84a 17 4 0 1 0 .13a .44 .83a .16 4 0 1 0 .04a .43 .77a .13 Ammonia evolution Mean Std. rate1 error 276. 68. ?a 3 116. 32. 9a 0 8 3 .26b .91 0 0 .18b .08 xMeans in each row with different superscript letters are significantly different (P < .05) . 2Rating on a scale of 1-15, 15 most offensive. 3Ranking of 3 samples, 3 most offensive. ------- Table 8. CORRELATIONS BETWEEN WATER, FECES, URINE CONTENT AND RATING, RANKING AND AMMONIA RELEASE RATE FOR MANURE SAMPLES INCUBATED FOR 24 HOURS AT 30° C Correlation Coefficients Rating Number Water -0.045 NS Fecal -0.154 NS Urine 0.109 NS Ranking Number Water -0.135 NS Fecal -0.234 .05 Urine 0.217 .05 Ammonia Release Rate Water -0.498 .01 Fecal -0.407 .01 Urine 0.584 .01 The ammonia release rates were positively correlated (P < .01) with the urine content of the samples. The water and fecal content were negatively correlated (P < .01) with the initial release of ammonia. The samples containing urine were ob- served to generate more ammonia (P < .05) than the samples containing only feces and water. EFFECT OF THE GRAIN SOURCE ON THE VOLATILIZATION OF AMMONIA AND HYDROGEN SULFIDE Methods Twelve Holstein replacement heifers were divided into three groups of four animals each. These animals were then fed rations based on three different grain sources (milo, corn, and barley) at three concentrations (25%, 50%, 75%) in a com- plete ration (Table 9). The animals were housed in the beef confinement units at Oregon State University during the experimental period. 32 ------- Table 9. COMPOSITION OF RATIONS1 FED REPLACEMENT HEIFERS TO DETERMINE THE EFFECT OF GRAIN SOURCE ON AMMONIA AND HYDROGEN SULFIDE GENERATION 25% Grain 50% Grain 75% Grain Barley Barley Alfalfa (chopped) Molasses, cane Cottonseed, meal Corn (rolled) Alfalfa (chopped) Molasses, cane Cottonseed, meal Milo (rolled) Alfalfa (chopped) Molasses, cane Cottonseed, meal 250 696 50 4 250 695 50 5 250 696 50 4 500 424 50 26 500 416 50 34 500 424 50 26 750 155 50 45 750 142 50 58 750 155 50 45 Nations calculated to be isonitrogenous on DP basis (DP = 9.6%) Fresh fecal samples were collected from the concrete floors of each of the respective pens and urine samples were col- lected from individual animals at random. Feces and urine from the same groups were then mixed in 300-ml Erlenmeyer flasks (50 g urine + 50 g feces) and incubated at 33° C in a water bath, and the volatilized ammonia and hydrogen sulfide were trapped. Duplicate samples were prepared for each of the feces and urine combinations. The samples were allowed to equilibrate for a period of 30 minutes in the water bath prior to being connected to their respective traps. During this time the head space gases were replaced at the rate of 0.33 1/min. At the_end of the flushing period the samples were connected to either the ammonia or hydrogen sulfide traps. 33 ------- The ammonia traps consisted of a series of two 25 x 200 mm test tubes containing 25 ml of boric acid C4% w/v) through which the displaced head space gases were bubbled at a rate of 0.33 1/min for a period of 22 hours. The boric acid traps were then combined and the ammonia content deter- mined using the Nesslerization method.55 The apparatus used in trapping the ammonia is shown in Figure 2. Hydrogen sulfide was trapped by bubbling the displaced head space gases through a series of two 25- x 200-mm test tubes, each containing 25 ml of Cd(OH)2 [2.7 g Cd(OH)2/l/ pH 9.5]. The tubes were painted black to prevent photodecomposition of the hydrogen sulfide. The hydrogen sulfide content of the samples was determined using the methylene blue method.56 Results and Discussion The hydrogen sulfide evolution rates were similar (P > .10) between samples from cattle fed the corn, barley, and milo based rations (Table 10). The hydrogen sulfide evolution rates from the 25% and 50% levels of supplementation of the three grains were not found to differ (P > .05). The 75% level of supplementation for each of the grains was similar with each of them being higher (P < .05) than their re- spective 25% and 50% levels. Table 10. EFFECT OF GRAIN SOURCE AND LEVEL OF SUPPLEMENTA- TION ON HYDROGEN SULFIDE GENERATION RATE BY MIX- TURE OF 50 g FECES AND 50 g URINE FROM REPLACEMENT HOLSTEIN HEIFERS FED VARIOUS GRAIN-BASED RATIONS Corn Mean1 25% 0.390a 50% 1.121a h 75% 4.96° Barley 25% 50% 75% Mean1 0 0 4 .616a .653a h .870° Milo 25% 50% 75% Mean1 0. 0. 4. 498a 741a K 53lb JMean values expressed as ug/hr. a' Means with different superscripts in the same columns are different (P < .05) . 34 ------- Ammonia was evolved at a much faster rate Capproximately 1,000 to 10,000 times) than hydrogen sulfide. Ammonia evolution rates were not different (P > .05) among the different levels of supplementation and the grains, with the exception of the 75% milo and the three barley based rations (P < .05), as shown in Table 11. Table 11. EFFECT OF GRAIN SOURCE AND LEVEL OF SUPPLEMENTA- TION ON AMMONIA EVOLUTION RATE BY MIXTURE OF 50 g FECES AND 50 g URINE FROM REPLACEMENT HOLSTEIN HEIFERS FED VARIOUS GRAIN-BASED RATIONS Mean1 Standard Error of Mean Corn 25% 3037.72a£ 424.33 50% 3467.41a? 401.46 75% 3189.17a£> 269.26 Barley 25% 3107.16a 527.89 50% 3921.13a 470.27 75% 3833.02a 322.23 Milo 25% 2925.89a£ 543.23 50% 2855.32ab 344.45 75% 2325.44° 233.24 *Mean value expressed as yg/hr. TU ' Means with common superscripts are not significantly different (P < .05) . 35 ------- RELATIONSHIP BETWEEN GRAIN SOURCE AND pH OF ANIMAL WASTE Methods Three different grain-based rations (corn, milo, and barley) were fed to groups of five Holstein replacement heifers. Each grain was fed at the 75% level. The composition of the rations is given in Table 9. After an initial ten-day adjustment period, feces and urine were collected from each of the groups. Samples containing 50 g of urine and 50 g of feces were prepared from each group. A total of 28 samples was evaluated for each of the groups at the rate of two samples/day. The samples were maintained in a water bath at 30° C. The apparatus and procedures used to trap the ammonia are de- scribed in the previous section. The boric acid traps were connected for a period of 22 hours, during which time head space gases were replaced at the rate of 0.33 1/min. After the incubation period the pH of the samples was determined using a Fisher Accumet Model 310 pH meter. The ammonia content of the combined double traps was determined using the method of Bremner and Kenney.57 Results and Discussion Results indicated that the grain source did alter the pH of the waste that was produced, and there was a significant correlation between the pH of the waste and the evolution rate of ammonia as shown in Table 12. There was a difference (P < .05) between the pH of the samples for each of the grains as indicated in Table 13, but differences in ammonia release were not (P > .05) noted between grains in the pooled data. Table 12. CORRELATIONS BETWEEN pH AND AMMONIA EVOLUTION RATES FOR CORN, BARLEY, AND MILO RATIONS Sample Correlation between pH P1 and ammonia evolution rate Corn 0.5022 .01 Milo 0.4204 .05 Barley 0.3838 .05 Correlation coefficients are significantly different at the probability level listed. 36 ------- Table 13. pH AND AMMONIA EVOLUTION RATES FROM FECES AND URINE MIXTURES FROM CORN, BARLEY, AND MILO RATIONS Sample Corn Milo Barley Average pH 7.21a 6.78b 7.65C Std error of mean .0634 .0839 .0871 Ave. ammonia evolution rate , mg/hr 2731. 96a 2602. 03a 3182. 48a Std error of mean 304.72 302.56 241.63 3 b C ' ' Means in the same column with different superscripts differ significantly (P < .05). EFFECT OF MOISTURE ON THE VOLATILIZATION OF AMMONIA AND AMINES Methods Samples of feces were collected from a group of Holstein re- placement heifers. The samples were then combined and sub- divided into two portions; one was immediately frozen and the dry matter (DM) content was determined (100° C for 24 hours) on the other (14.8% DM). A fresh urine sample was then collected which was later determined to have a nitrogen content of 0.28%. The fresh urine and feces with DM of 14.8% were then mixed to form duplicate samples containing 95% and 99% moisture. The 95% moisture samples contained 50 g feces, 24 g urine, and 75 g water. The 99% moisture samples contained 50 g feces, 24 g urine, and 670 g water. The samples were maintained in a water bath at 37° C for the 14-day experimental period. The total volumes were adjusted to their original volume on a daily basis by adding dis- tilled water to replace evaporative losses. The apparatus used for trapping the ammonia and amines is shown in Figure 3. Air from a laboratory air outlet was bubbled through a dilute HC1 trap (1:15 cone. HCl to dis- tilled water) before displacing the head space gases of the samples to remove any ammonia or amines that might be 37 ------- BORIC ACID WATER BATH 00 Figure 3. Apparatus used to trap evolved ammonia and amines. ------- present. The head space gas of each of the samples was replaced at the rate of 0.33 to 0.4 1/min and then bubbled through a boric acid trap to remove the ammonia and amines. Traps were changed every 24 hours. Total volatile nitrogen and amine evolution rate were then determined for each sample. The method described by Ekladius and King58 using butylamine as a standard was used for the amine assay. The total nitrogen was determined by the semi-micro-Kjeldahl method of Bremner and Kenney57 and expressed as ammonia. Results and Discussion Amines were evolved at the rates of 17.86 and 16.41 ug/day for the 95% and 99% moisture levels, respectively, which was 0.11% of the total nitrogen volatilized. Ammonia evolution rates were 15.15 and 13.20 yg/day for the 95% and 99% moisture samples, respectively. The ammonia and amine evolution rates had a significant negative correlation with the length of storage (Table 14) and ammonia and amine release rates were found to be positively correlated (P < .01) to each other. This would support the idea expressed by Merkel e_t al. 22 that ammonia was a precursor of amines. EFFECT OF FECES, URINE, WATER, AND STORAGE PERIOD ON AMMONIA RELEASE Methods Fresh feces and urine were collected, as described earlier, from Holstein replacement heifers which were fed a base ration containing 25% barley and 75% alfalfa hay (Table 8). A composite was made for both the urine and feces. Dupli- cates of the following samples were then prepared: 100% feces; 100% urine; 50% feces +50% urine; 75% feces + 25% urine; 75% feces + 25% water; 50% feces + 50% water; 25% feces + 75% water; and 5% feces + 95% water; all samples contained 100 g of material. The samples were maintained in a water bath at 30° C for a period of 25 days. The trapping procedure was the same as described previously. The head space gases were replaced at the rate of 0.33 1/min and trapped for a period of 3 hours; two trapping periods were carried out each day on each of the samples. The ammonia evolution rate of the samples was then determined using the method of Bremner and Kenney57 and expressed as ammonia. 39 ------- Table 14. CORRELATIONS BETWEEN MEAN AMMONIA AND AMINE EVOLUTION RATES AND STORAGE PERIOD Correlation Evolution rate (10-6 g/hr) Amine 95% moisture Amine 99% moisture Ammonia 95% moisture Ammonia 99% moisture Ammonia 95% moisture Ammonia 99% moisture Other Variable Storage time Storage time Storage time Storage time Amine evolution Amine evolution Correlation coefficient -0.771 -0.538 -0.727 -0.783 0.903 0.822 P1 0.01 0.05 0.01 0.01 0.01 0.01 Correlation coefficients are significant at the probability listed. Results and Discussion Average ammonia evolution rates for the various samples are given in Table 15. Ammonia was evolved at a faster rate from samples containing urine (P < .05) than the samples containing only feces and water. Correlation coefficients between the ammonia release rates and length of storage for the various samples are given in Table 16. The samples containing feces only and feces plus water were found to be positively correlated (P < .01) with the time of storage except for the 5% feces +95% water samples. 40 ------- Table 15. EFFECTS OF VARIOUS LEVELS OF FECES, URINE AND WATER ON AVERAGE AMMONIA EVOLUTION RATES (yg/hr) Sample Average Ammonia evolution rate, ug/hr Standard Error of Mean 100% Feces 100% Urine 50% Feces 50% Urine 75% Feces 25% Urine 75% Feces 25% Water 50% Feces 50% Water 25% Feces 75% Water 5% Feces 95% Water 3. 426. 119. 15. 3. 6. 9. 2. 15a 35b 43C 64a 42a 61a 71a 25a 0 90 10 4 0 1 1 0 .92 .39 .69 .96 .79 .25 .45 .87 3. b C ' ' Means with different superscripts are different (P < .05) . Samples containing only urine were observed to have a rapid release of ammonia between the 2nd and 5th day of storage as shown in Figure 4. The feces plus water samples showed no rapid initial release of ammonia but increased as the storage period increased. The combination of feces and urine samples showed a rapid initial release of ammonia, then a decrease at day 5 until day 15, and then a gradual in- crease continuing until the end of the 25-day period. 41 ------- Table 16. CORRELATIONS BETWEEN AVERAGE AMMONIA EVOLUTION RATE AND LENGTH OF STORAGE Sample Correlation Coefficient1 P 2 100% Feces 100% Urine 50% Feces 50% Urine 75% Feces 25% Urine 75% Feces 25% Water 50% Feces 50% Water 25% Feces 75% Water 5% Feces 95% Water 0 -0 -0 -0 0 0 0 -0 .572 .192 .152 .680 .635 .503 .636 .134 .01 NS NS .01 .01 .01 .01 NS Calculated on the ammonia evolution rate vs the number of days on trial. Correlation coefficients are significantly different at the probability level listed. Urine was found to be primarily responsible for the initial release of ammonia; feces had little effect. Approximately 100 times more ammonia was evoluted per gram from urine than from feces. The fecal material was found to increase the amount of ammonia released with increased time, but feces only accounted for a small portion of the total ammonia released. The results would indicate that urea is hydro- lyzed more rapidly to ammonia than fecal proteins, and that urinary urea plays an important role in the volatilization of ammonia from animal wastes. 42 ------- Ul 100% URINE 50% 'FECES ^ .054- 0 / 100% FECES 0 1 i i i i P i 10 15 TIME (DAYS ) 20 25 Figure 4. Ammonia evolution rate for urine, feces, and combination as a function of time. ------- EFFECT OF VARIOUS ANIMAL WASTE CHARACTERISTICS ON THE EVOLUTION OF AMMONIA AMD VOLATILE NITROGEN GASES Methods Two groups of five Holstein replacement heifers were fed barley-based rations that contained three levels of barley (25%, 50%, 75%) formulated into complete rations (Table 8). The groups were started on the 25% ration, then changed to the 50%, and then to the 75%; each ration was fed ad libitum for a period of 15 days. Urine and feces collected from each of the individual animals were combined (50 g of urine + 50 g of feces) and placed in a 300-ml Erlenmeyer flask and mixed thor- oughly. These samples were placed in a water bath main- tained at 30° C. The trapping procedure described pre- viously was used. The ammonia released from the samples was trapped for a period of 3 hours. The following analyses were performed: dry matter and crude protein content of the feces; specific gravity and urea content of the urine; and ammonia and total volatile nitrogen evolved. The dry matter content was determined by drying a fecal sample for a period of 24 hours at 100° C. The crude protein was determined by using the micro-Kjeldahl method.57 The ammonia was determined by taking a 10-ml portion of the combined boric acid traps for each of the samples and using the micro-Kjeldahl method starting with the distillation step. Total volatile nitro- gen (expressed as ammonia) was determined by taking a 5-ml aliquot of the boric acid trap and using the procedure as described for crude protein. The Hycel urea nitrogen method59 was used to measure the urea content of the urine samples. The urinometer was used to measure the specific gravity of the urine samples. Results and Discussion The feeding trial was divided into five periods: 25% barley; transition period between 25% and 50% barley; 50% barley; transition period between 50% and 75% barley; and the 75% level. The means and standard error of the means are given for each of these periods in Tables 17, 18, and 19. The correlations between the variables and total volatile nitrogen evolution rates are given in Table 20. The dry matter and crude protein content of the samples were found to have no effect (P > .10) on the initial rate of ammonia release. 44 ------- Table 17. RESULTS OP FECAL MATTER ANALYSES FOR TEN HEIFERS FED RATIONS OF 25, 50, and 75 PERCENT BARLEY Dry Matter Crude Protein Percent barley Mean percent Standard error Mean percent Standard error 25 18.95 0.25 10.28 0.339 Transition 25-50 19.34 0.269 9.47 0.35 50 20.0 0.27 10.8 0.58 Transition 50-75 75 21.38 20.15 0.36 0.80 11.08 11.01 0.35 0.55 The ammonia and total volatile nitrogen evolution rates were highly correlated (P < .01) as determined by analysis of the boric acid traps. Urea content of the urine was related to the ammonia evolution rate (P < .01). The urea content of the urine was found to be correlated (P < .01) with the specific gravity values of the urine. This would explain why the specific gravity was correlated (P < .01) with the ammonia evolution rates for the samples. SUMMARY The olfactory evaluation of the waste produced by animals fed essential oils showed that the offensiveness of odors associated with fresh waste can be modified with the addition of an essential oil source. The addition of pepper- mint oil (0.25% of the diet) significantly reduced the relative offensiveness associated with the waste. This modification seemed to be a masking effect directly related to compounds excreted in the urine; it was not associated with the feces. Sagebrush supplemented at the 1% and 1.5% levels did not show any alteration of the olfactory evalua- tion. These results do not agree with the Colorado work, but the levels of supplementation were lower and the con- centrations of essential oils in the sagebrush varieties used may have been different. 45 ------- Table 18. AMMONIA AND TOTAL VOLATILE NITROGEN EVOLUTION RATES FOR MANURE SAMPLES PROM TEN HEIFERS FED RATIONS OF 25, 50, and 75 PERCENT BARLEY Ammonia evolution rate Percent barley 25 Transition 25-50 50 Transition 50-75 75 Mean 10- 6 g/hr 8.14 10.9 14.62 16.25 10.06 Standard error 1.06 0.99 1.03 1.39 1.86 Total volatile nitrogen evolution rate Mean 10" 6 g/hr 9.9 11.09 15.93 17.85 10.43 Standard error 0.57 0.91 1.00 1.53 0.64 ------- Table 19. RESULTS OF URINE ANALYSES FOR TEN HEIFERS FED RATIONS OF 25, 50, and 75 PERCENT BARLEY Percent barley Urea content Mean Standard mg/1 error Specific gravity Standard Mean error 25 Transition 25-50 50 Transition 50-75 75 848.9 801.6 737.7 793 896 46.5 85.9 49.9 48.4 177 1.032 1.023 1.028 1.024 1.025 0.00122 0.00184 0.00127 0.00129 0.00399 The results indicate that the cereal grain source and level in a ration does affect the initial volatilization of hydrogen sulfide and volatile nitrogenous gases. The pri- mary effect of the grain source and level seems related to the pH of the wastes produced, which in turn affects the subsequent release of basic volatile nitrogenous gases. The ammonia release rate was found to be approximately 1,000 times greater than the hydrogen sulfide release rate at the 75% level of grain supplementation and 10,000 times greater at the 25% and 50% levels. This change in the relative amounts of hydrogen sulfide and ammonia was thought to be due to changes in the pH of the wastes. The three different cereal grains evaluated were responsible for some pH differences. The waste produced from the milo-based ration (75% of the diet) was found to have a significantly lower pH than that from the barley or corn fed animals. This is important with respect to ammonia release because there is a direct relationship between ammonia release rate and pH. 47 ------- Table 20. CORRELATIONS BETWEEN AMMONIA EVOLUTION RATES AND UREA, CRUDE PROTEIN, DRY MATTER, TOTAL VOLATILE NITROGEN AND SPECIFIC GRAVITY OF URINE SAMPLES AND BETWEEN UREA CONTENT AND SPECIFIC GRAVITY OF URINE Correlation coefficient P1 Correlation between ammonia evolution rate and Dry matter content of feces 0.0159 NS Crude protein content of feces 0.0081 NS Total volatile nitrogen 0.8784 .01 evolution rate Urea content of urine 0.3123 .01 Specific gravity of urine 0.2700 .01 Urea content of urine Specific gravity of urine 0.2659 .01 Correlation coefficients are significantly different at the probability level listed. The addition of water to manure was found to reduce the evolution rate of ammonia and amines during the initial storage period. This was attributed to the capacity of water to absorb ammonia and reduce its volatilization rate. The ammonia evolution rate was negatively correlated with length of storage period for urine fecal matter mixtures. This indicates that major nitrogen enrichment o.f the atmosphere would occur during the first phase of the storage period. The major contributor to the evolved ammonia is the urea content of the waste. Approximately 100 times more ammonia was evoluted per gram from urine than from feces. The evolution of ammonia from urine was rapid, while the feces showed a more prolonged release, accounting for a small portion of the total ammonia volatilized from the waste. 48 ------- Of the variables measured, it was found that urea, specific gravity, and moisture content of the waste were the most highly correlated with volatilization of nitrogenous gases. The modification of bovine rations has shown that changes in waste characteristics can be produced. Further research is needed to determine how practical this type of approach would be in controlling the volatilization of gases and odors from bovine confinement production units. 49 ------- SECTION VI AMMONIA EVOLUTION RATE FROM VARIOUS SURFACES ASSOCIATED WITH LIVESTOCK PRODUCTION Ammonia release from manure-covered surfaces, or surfaces which are in the immediate proximity of livestock production facilities, has been demonstrated. Koelliker and Miner12 documented the release of ammonia from an anaerobic swine manure lagoon surface. Ammonia concentrations in air near livestock feeding operations have been measured as signif- icantly higher than those in other agricultural areas. Due to the solubility of ammonia in water, the potential exists for livestock production enterprises to make significant contribution to the nitrogen content of surface impound- ments, thereby contributing to enrichment. RATE MEASURING DEVICE In order to quantify the rate of ammonia release from sur- faces associated with livestock production systems, the sampling box shown schematically in Figure 5 was constructed. This box covers a square area 0.61 m on a side. There is a plywood deck 0.3 m from the bottom of the box. A dia- phragm pump pulls air from beneath the deck through ab- sorption tubes and finally through a wet test meter for air volume measurement. Air is admitted to the space beneath the deck through a copper tube which terminates in a can filled with activated carbon. The activated car- bon insures that ammonia-free air enters the system. A metal strip attached to the lower edge of the sampling box prevents the entrance of unfiltered air. The air pump was driven by a 12-volt battery and DC-AC converter when other electrical connections were not accessible. 50 ------- 0.6 M 1. Activated carbon filtered air inlet. 2. Diaphragm air vacuum pressure pump. 3. Gas impinger tubes with absorption material. 4. Wet test meter. 5. Metal sealing strip. 6. Lid for rain protection. Figure 5. Construction of the sampling box to capture the released volatile compounds from a soil surface previously exposed to animal manures. 51 ------- Solid Surface Rate Measurements The sampling box was used to measure ammonia release rates from a variety of surfaces associated with. the OSU Dairy, Swine Center, and campus. Each of the sampling locations was subject to a variety of short-term variations and precise values were not reproducible. By collecting five or more samples from forty locations, useful information was obtained. Values were measured under summer conditions of 20° C to 30° C daytime temperatures during a period without rainfall. The results are summarized in Table 21. Table 21. EVOLUTION RATE OF AMMONIA FROM SEVERAL DIFFERENT SURFACES IN THE VICINITY OF LIVESTOCK PRODUCTION FACILITIES Evolution rate, Surface description mg/day-m2 On pasture grass and bare soil more 1-2 than 30 m from dairy barn On pasture with dried manure and on 2-5 manure-free dairy barn surfaces Pasture land after recent liquid dairy 5-20 manure application Manure-covered aisle in freestall 50 - 100 dairy barn Grassland near swine barn with no 2-3 direct manure contact Soil and grass with some previous 2-5 manure application Lagoon water 20 - 100 Campus sidewalk and lawn surfaces 0.5 - 1.5 52 ------- A lagoon surface releasing 25 mg/m2-day would release approximately 90 kg/ha. C8Q Ib/acre) annually. This value is considerably smaller than anticipated. This is best explained by the relatively low pH (7.9) of this lagoon for ammonia desorption. At this pH, less than four percent of the ammonia is present as NH3 and exhibiting a vapor pressure, The same explanation - low soil pH - also explains the low ammonia release rates measured in this study. Nitrogen flux rates ranging from 25 to 80 mg/m2-day have been reported from a grazed alfalfa pasture. This technique offers a simple quantitative technique for the measurement of ammonia release rates from surfaces associated with livestock production. The values measured correlate well with observed odor release and lead to a prediction of the potential contribution of livestock feedings to airborne plant nutrients which can be absorbed by nearby surface waters. Lagoon Surface Rate Measurements At various times during the summer, the rate of ammonia volatilization was measured from an anaerobic swine manure lagoon. Apparatus for measurement consisted of a bucket 45 cm tall with an interior diameter of 30 cm, covered with a wooden plate. The bucket was filled approximately one- half full of lagoon water. Air was pumped from inside the bucket and bubbled through a weak acid solution to trap the ammonia. Air was replaced into the bucket one-half full of lagoon water. Results are shown in Table 22. An intended goal of this experiment was to find how various additives and barriers affected the rates of ammonia vola- tilization of the swine lagoon water. Ten buckets, with interior diameter of 28.4 cm and height of 35 cm, were used. Five buckets were filled to 20 cm with lagoon water. The remaining five were filled with fresh water and manure. Readings were taken using a sealed cover placed over each bucket. Air was pumped through a weak acid solution to trap the ammonia from within the bucket cover. Air was _ replaced through a charcoal filter. Results are noted in Table 23. 53 ------- Table 22. AMMONIA EVOLUTION PROM ANAEROBIC LAGOON WATER MEASURED DURING THE SUMMER OF 1975 Date Temperature, 0 C Ammonia evolution rate, mg/day-m2 6-18 7-08 7-11 7-18 7-29 8-12 8-15 8-19 8-20 8-22 21 23 26 23 21 21 21 21 20 22 52 106 151 86 67 84 70 50 62 60 Table 23. AMMONIA EVOLUTION FROM ANAEROBIC LAGOON WATER AND FRESH MANURE AND WATER WHEN ADDITIVES ARE USED Additive Control Acid added mg/m 1. 0. Fresh 2-hr 84 85 influent % of control 46 mg/m 1. 1. Lagoon 2-hr % 96 17 water of control 60 to bring pH to 6 Oil covering 0.41 surface Micro-aid 0.49 (Odor con- trol agent) S tyro foam 0.91 beads cover- ing surface 22 27 49 0.40 1.05 1.29 20 53 66 54 ------- Disposal Field Rate Measurements Considerable interest exists in evaluating the nitrogen loss when manure is applied to crop land. To meet this need, anaerobic lagoon effluent was applied to a pasture plot at a rate equivalent to 200 kg of nitrogen per ha. Prior to application, the plot was evolving ammonia at a rate of 1.0 mg/m2-day. The pH of the soil was 4.5. Immediately after application, the plot evolution increased to 4.0 mg/m2-day for a six-hour period, then returned to the original value. The adjacent plot ammonia evolution rate also rose in response to the application of an equal volume of water. Thus, in this particular case, the nitrogen loss was very small. Swine Enterprise Measurements Atmospheric ammonia content was monitored in the vicinity of a 1,000-head commercial hog operation with surrounding land in grass seed production. The intended purpose was to look at the effects of several parameters on atmospheric ammon ia. Sulfuric acid sampling beakers were placed in covered stations in a pattern around the operation up to distances of one km. The ammonia level was determined by Nesslerization. Data was put in the form of mg-NH3/m2-day to express the amount of ammonia absorbed across the solution surface per day. Growth of the rye grass correlated with ammonia concen- tration. During the early growth period, absorption rates ranged from 2 to 5 mg-NH3/m -day. This increased to a range of 3 to 6 mg-NH3/m2-day. Immediately after the grass was cut, absorption rates jumped to a range of 4 to 11 mg/m -day. Weather fluctuations seemed to influence ammonia level to some degree. Hot, humid weather seemed to cause higher levels than cold temperatures. Periods following rain showed the atmospheric ammonia levels to be slightly lower. Wind also seemed to disperse the ammonia so that lower atmospheric concentrations were experienced. During the testing period, one area was sprayed with manure slurry from a storage pit. As expected, this area showed higher atmospheric concentrations. In general, the atmo- spheric concentrations became smaller in inverse proportion to the distance from the source. 55 ------- EVOLUTION MEASUREMENTS IN THE LABORATORY A series of laboratory experiments have been conducted in an attempt to document the production of gases by stored manure as well as the potential of various gas absorption techniques to remove odorants. Those results are reported below. Effect of Moisture Content Dairy manure samples of four solids contents (0.5, 1.5, 16, and 24 percent) were placed in flasks and air passed over the samples. The flask containing the nonadjusted moisture content (16 percent) produced the greatest concentrations of both ammonia and hydrogen sulfide. Addition of excess water appeared to absorb and retain the gases while drying in- hibited their production. Use of Water as an Absorbent This experiment was designed to examine the hypothesis that water could be used to absorb odorants from air laden with gases from manure decomposition. The ammonia and COD concentration reductions achieved in the column were con- firmed by personal observation of a decreased intensity when entering and exit stream odors were compared. The apparatus used is shown in Figure 6. Data collected during this experiment are presented in Table 24. Use of Natural Ammonia Absorbents This experiment was designed to demonstrate ammonia removal from air by normal environmental absorbents water, soil, and grass. A single carboy of manure was used as the odor source. Air was pumped from this carboy and split into absorbing flasks as shown in Figure 7. For absorption, odorous air was passed over the water and through the other two media. This preliminary experiment indicated that all three media effectively reduced the ammonia content when first used. The grass rapidly lost effectiveness as it dried and began to release ammonia as it decomposed and as mold growth became evident (Table 25). A second experiment similar to the above was made, except that the odorous air was passed over the absorbing media rather than through them. Again, as indicated in Table 26, all three media were initially effective in removing ammonia. As the soil and grass began to dry and decompose, their effectiveness decreased. 56 ------- Distilled Water Reservoir, pH 6 Air Discharge Air Pump -\ Manure Sample Collected Water Figure 6. Laboratory apparatus used to evaluate the absorption of odorants using contact with water in a counter current exchange column. 57 ------- Table 24. ABSORPTION OF AMMONIA FROM MANURE GASES BY WATER IN A COUNTER CURRENT EXCHANGE COLUMN Air stream Date of observation Ammonia concentration (% reduction) COD concentration (% reduction) Water stream Ammonia concentration 11-28-73 11-29-73 11-30-73 12-03-73 12-04-73 12-05-73 12-06-73 12-08-73 12-10-73 12-11-73 12-12-73 12-13-73 12-14-73 12-17-73 12-18-73 28 7 51 48 64 14 9 63 55 56 18 9 32 50 40 8 -9 6 2 23 23 16 -132 44 21 22 24 18 14 -85 .159 .283 .172 .089 .150 .137 .083 .205 .150 .135 .107 .154 .134 .160 .160 .206 .343 .188 .132 .113 .097 .120 .130 .230 .177 .123 .218 .203 .175 .159 FEEDLOT ODOR STUDY Ammonia evolution and absorption rate measurement techniques developed in pursuit of this project were utilized in a feedlot odor evaluation project conducted during the summer of 1975. The feedlot odor project was funded in part by the National Science Foundation, Research Applied to National Needs, Grant No. ESR 74-23211, the Idaho Department of Health and Welfare, and the host feedlot. A final report on this project has been published by the Idaho Research Foundation. That report is summarized below. Alternate techniques for the control of odors from a cattle feedlot were evaluated at a southeastern Idaho site. Three separate odor sources were present: the feedlot surface, the runoff collection and storage ponds, and a potato waste 58 ------- AIR PUMP MANURE SLURRY Figure 7. Laboratory apparatus used to evaluate the ability of various absorbing materials to remove ammonia from odorous air. 59 ------- Table 25. AMMONIA IN AIR AFTER PASSING OVER WATER, THROUGH GRASS, SOIL OR NOTHING (mg/day) Absorbing media Date Water Grass Soil Nothing 3-18-74 3-19-74 3-20-74 3-21-74 3-22-74 3-25-74 3-26-74 3-27-74 0.11 0.29 0.13 1.08 1.00 1.12 4.44 62.4 58.8 0.16 0.11 1.12 2.80 10.08 3.08 0.124 3.96 5.20 4.64 Media replaced in all four flasks 3-28-74 3-29-74 4-01-74 4-02-74 4-03-74 4-04-74 4-05-74 4-08-74 - - - 0.144 0.80 1.76 0.22 0.40 0.56 1.08 1.68 1.72 9.68 38.00 288.00 0.17 0.15 - 0.14 - 0.12 0.10 2.32 4.96 5.12 7.20 9.76 19.60 25.2 21.60 storage pit. Potato wastes from nearby processing plants were included in the ration at this feedlot after storage in a concrete-lined pit. The storage pit made a significant contribution to odor release but due to its unique character, was not included in the study. Nine products were applied to various feedlot pen surfaces at rates and frequencies suggested by the respective manu- facturers. Ammonia release rates and odor intensities of the feedlot litter were used as measures of success. Four of the products, sodium bentonite, ODOR CONTROL PLUS, and the two natural zeolites were found to consistently reduce the rate of ammonia release from treated areas when compared to nearby untreated areas. Odor intensity measurements confirmed the effectiveness of sodium bentonite. The ODOR CONTROL PLUS treated pen had a measurably less intense odor 60 ------- Table 26. AMMONIA IN AIR AFTER PASSAGE OVER WATER, GRASS, SOIL, OR NOTHING (mg/day) Absorbing media Date Water Grass Soil Nothing 4-16-74 4-17-74 4-18-74 4-19-74 4-22-74 4-23-74 4-24-74 4-25-74 4-26-74 .11 - .46 .22 .19 .12 .29 .29 .26 0.19 0.36 0.82 1.92 4.5 3.8 2.9 9.8a 18. 4a 0.16 0.40 0.72 0.48 5.6 2.4 4.2 2.7 3.1 13.2 9.6 16.0 2.64 17.6 9.6 12.0 8.0 9.2 ^composition of the grass was evident, causing a release of ammonia. five days after treatment but not ten. Only one of two observers was able to distinguish the zeolite treated pen litter from the control. The cost of the effective materials ranged from $150 to $300 per ha for treatment during the odor production season. Two materials were added to the feed ration as potential odor control techniques; however, neither material proved effective based upon the ammonia release rate or odor intensity measurements made. A green belt odor barrier was established along the two sides of the feedlot where odor control is essential. Three species of trees and shrubs were planted in a typical wind-break manner. The success of this procedure will be evident only as the plantings mature and reach an effective height. A spray system was installed in the same area as the plantings. The spray system was designed to create a mist extending 6 m into the air along these borders. Although difficult to evaluate in a highly variable natural setting, the data suggested a more rapid decrease in ammonia absorption rate with downwind distance when the water spray was in operation than at other times. This_system is effective only under low velocities, which is also the time of greatest odor transport. 61 ------- The spray system was also used to dispense a dilute potassium permanganate solution. The first effort was to demonstrate the practice would not damage wetted vegetation. When applied at concentrations below 74 mg/1, no plant effects were noted. When added to the spray at 10 trtg/1, potassium permanganate seemed to further speed the odor intensity re- duction with distance; however, substantiation of that re- sult will require considerably more data than it was possible to accumulate during this study. Although not included in the original plan for this project due to the experimental difficulties anticipated, two chemicals were sprayed on the runoff retention ponds as an odor control effort. Ammonia absorption rates and hydrogen sulfide concentrations were the measurement techniques used. The close proximity of the ponds to one another and to the feedlot as well as the variability ifi climatic conditions made evaluation difficult; hence, no conclusions could be drawn. Further experimentation is necessary. Examination of the climatic data indicate that for the Blackfoot, Idaho, area, climatic conditions would transport odor from the Harding Feedlot toward the koreland community approximately three percent of the time. This frequency was, in general, confirmed by the odor records maintained by the residents of the area. 62 ------- SECTION VII REFERENCES 1. Schlossing, T. Determination of Atmospheric Ammonia. Compt. Rend. 80^:175-178, 265-268, 1875. 2. Weatherby, J. H. Chronic Toxicity of Ammonia Fumes by Inhalation. Proceedings, Soc. Exptl. Biol., 1952. 8_1:300. 3. Anderson, D. P., R. R. Wolfe, F. L. Cherms, and W. E. Roper. Influence of Dust and Ammonia on the Develop- ment of Air Sac Lesions in Turkeys. Am. J. Vet. Res. 2£:1049-1058, 1968. 4. Charles, D. R. and C. G. Payne. The Influence of Graded Levels of Atmospheric Ammonia on Chickens. British Poultry Sci., 7:177, 1966. 5. Boyd, E. M., M. L. MacLachlan, and W. F. Perry. Ex- perimental Ammonia Gas Poisoning in Rabbits and Cats. J. Ind. Hyg. Toxicol. 2^:29, 1964. 6. Hutchinson, G. L. and F. G. Viets, Jr. Nitrogen En- richment of Surface Water by Absorption of Ammonia Volatilized from Cattle Feedlots. Science. 166:514, 1969. 7. Luebs, R. E., K. R. Davis, and A. E. Laag. Enrichment of Atmosphere with Nitrogen Compounds Volatilized from a Large Dairy Area. J. Envir. Qual. 2_(~L) :137, 1973. 8. McCalla, T. M. and F. G. Viets, Jr. Proceedings, Pollution Research Symp., University of Nebraska, May 23, 1969. 63 ------- 9. Stephens, E. R. Identification of Odors in Feedlot Operations. Environmental Protection Agency Publication SW-5r.2, 1971. 24 p. 10. Miner, J. R. and T. E. Hazen. Ammonia and Amines: Components of Swine-Building Atmosphere. Trans. Amer. Soc. Agr. Engr. 12(6) : 772-774 , 1973. 11. Ryan, J. A. and D. R. Kenney. Ammonia Volatilization from Surface Applied Wastewater Sludge. J. Water Poll. Control Fed. 1975. 12. Koelliker, J. K. and J. R. Miner. Desorption of Ammonia from Anaerobic Lagoons. Trans. Amer. Soc. Agr. Engr. 16_(1):148, 1973. 13. Stewart, B. A. Volatilization and Nitrification of Nitrogen from Urine Under Simulated Cattle Feedlot Conditions. J. Envir. Sci. and Tech. 4_(7) :579-582, 1970. 14. Elliott, L. F., G. E. Schuman, and F. G. Viets, Jr. Volatilization of Nitrogen-Containing Compounds from Beef Cattle Areas. In: Proceedings, Soil Sci. Soc. Amer., 1971. 35_:752. 15. Adriano, D. C., A. C. Chang, and R. Sharpless. Nitrogen Loss from Manure as Influenced by Moisture and Tempera- ture. J. Envir. Qual. 3^(3) :258, 1975. 16. Ludington, D. C., A. T. Sobel, and A. G. Hashimoto. Odors and Gases Liberated from Diluted and Undiluted Chicken Manure. Paper No. 69-426. Amer. Soc. Agr. Engr. 1969. 17. Luebs, R. E., K. R. Davis, and A. E. Laag. Diurnal Fluctuation and Movement of Atmospheric Ammonia and Related Gases from Dairies. J. Envir. Qual. _3(3) :265, 1974. 18. Miner, J. R. Odors from Confined Livestock Production. Environmental Protection Technology Series. EPA-660/2- 74-023, 1974. 125 p. 19. Chao, T. and W. Kroontje. The Relationships Between Ammonia Volatilization, Ammonia Concentration and Water Evaporation. In: Proceedings, Soil Sci. Soc. Amer., 1964. 28:393. 64 ------- 20. Viets, F. G., Jr. Symposium on Agriculturally Related Pollution and Fertilizer Conference. Bozeman, February 1970. p. 11-16. 21. Earth, C. L. and L. B. Polkowski. Identifying Odorous Components on Stored Dairy Manure. Trans. Amer. Soc. Agr. Engr. r?(4) : 737-740 , 1974. 22. Merkel, J. A. , T. E. Hazen, and J. R. Miner. Identi- fication of Gases in a Confinement Swine Building Atmosphere. Trans. Amer. Soc. Agr. Engr. 12 (3) .-310-315, 1969. 23. Leonardos, G. , D. A. Kendall, and N. J. Barnard. Odor Threshold Determinations of 53 Odorant Chemicals. J. Air Poll. Control Assoc. 19_:91, 1969. 24. White, R. K., E. P. Taiganides, and G. Cole. Chromato- graphic Identification of Malodors from Dairy Animal Waste. In: Proceedings, Inter. Symp. of Livestock Wastes. St. Joseph, Amer. Soc. Agr. Engr., 1971. 25. Luebs , R. E., A. E. Laag, and K. R. Davis. Ammonia and Related Gases Emanating from a Large Dairy Area. Calif. Agr. r7(2) :10, 1973. 26. Burnett, W. E. and N. C. Dondero. Microbiological and Chemical Changes in Poultry Manure Associated with De- composition and Odor Generation. In: Proceedings, Cornell University, Conf. on Agr. Waste Mgmt., 1969. p. 271. 27. Mosier, A. R. Effect of Cattle Feedlot Volatiles, Aliphatic Amines, on Chlorella Ellipsoidea Growth. J. Envir. Qual. ,3(1):26-30, 1974. 28. Day, D. L. , E. L. Hansen, and S. Anderson. Gases and Odors in Confinement Swine Buildings. Trans. Amer. Soc. Agr. Engr. 8^:118, 1965. 29. Hammond, W. C. , D. L. Day, and E. L. Hansen. Can Lime and Chlorine Suppress Odors in Liquid Hog Manure. Agr Engr. 4!?: 340, 1968. 30. Curtis, S. E. The Pig's Air Environment in Enclosed Accommodations. Feedstuffs. £7(11), March 1975. 31. Taiganides, E. P. and R. K. White. The Menace of Noxious Gases in Animal Units. Trans. Amer. Soc. Agr. Engr. 12:359, 1969. 65 ------- 32. Burnett, W. E. Air Pollution from Animal Wastes- Determination of Malodors by Gas Chromatographic and Organoleptic Techniques. Envir. Sci. Tech., ^3:744, August 1969. 33. Bethea, R. M. and R. S. Narayan. Identification of Beef Cattle Feedlot Odors. Trans. Amer. Soc. Agr. Engr. 15:1135, 1972. 34. Avery, G. L., G. E. Merva, and J. B. Gerrish. Hydrogen Sulfide Production in Swine Confinement Units. Trans. Amer. Soc. Agr. Engr. 1JJ(1) :149, 1975. 35. Burnett, W. E. and A. T. Sob«l. Odors, Gases, and Particulate Matter from High Density Poultry Manage- ment Systems as They Relate to Air Pollution. Depart- ments of Food Science and Agricultural Engineering, Ithaca, N.Y. Progress Report No. 1, N.Y. State Con- tract No. 1101. 1967. 36. Merkel, J. A. Atmospheric Composition in an Enclosed Swine Production Building. Unpublished Ph.D. thesis, Ames, Iowa State University Library, 1967, 37. Frus, J. D., T. E. Hazen, and J. R. Miner. Chemical Oxygen Demand of Gaseous Air Contaminants. Trans. Amer. Soc. Agr. Engr. 1£(5) :837, 1971. 38. Mosier, A. R., C. W. Andie, and F. G. Viets, Jr. Identification of Aliphatic Amines Volatiles from Cattle Feedyard. J. Envir. Sci. and Tech. 7^(7) :642- 644, 1973. 39. Day, E. A., D. A. Forss, and S. Patton. Identification of Volatile Components by Gas Chromatography and Mass Spectrometry. J. Dairy Sci. £1:932, 1958. 40. Rasmussen, R. A. Analysis of Trace Organic Sulfur Compounds to Air. American Laboratory, p. 55-61, December 1972. 41. Zlatkis, A., H. A. Lichtenstein, A. Tishbee, W. Bertsch, F. Shunbo, and H. M. Liebich. Concentration and Analy- sis of Volatile Urinary Metabolites. J. Chromatographic Sci. 11:299-302, 1973. 66 ------- 42. Miller, A., Ill, R. A. Scanlan, J. S. Lee, and L. M. Libbey. Volatile Compounds Produced in Sterile Fish Muscle (Sebastes melanops) by Pseudomonas putrefaciens, Pseudomonas fluorescens, and an Achromobacter Species. Applied Micro, p. 18-21, July 1973. 43. Rudinsky, J. A., M. Morgan, L. M. Libbey, and R. R. Michael. Sound Production in Scolytidae; 3-methyl- 2-cyclohexene-l-one Released by the Female Douglas Fir Beetle in Response to Male Sonic Signal. Environ- mental Entomology. 2_(4) , August 1973. 44. Hartung, L. D. , E. G. Hammond, and J. R. Miner. Iden- tification of Carbonyl Compounds in a Swine-Building Atmosphere. In: Proceedings, Inter. Symp- of Live- stock Wastes. Amer. Soc. Agr. Engr., Pub. SP-271. 1971. p. 105-107. 45. Suffis, R. and D. E. Dean. Identification of Alcoholic Peaks in Gas Chromatography by a Non-Aqueous Extraction Technique. Anal. Chem. 3£:480-483, 1972. 46. Hammond, E. G. , G. A. Junk, P. Kuczala, and J. Kozel. Constituents of Swine House Odors. In: Proceedings, Inter. Livestock Envir. Symp. Amer. Soc. Agr. Engr., SP 01-74. 1974. p. 364-372. 47. Junk, G. A. and H. J. Svec. The Use of Macroreticular Resins in the Analysis of Water for Trace Organic Con- taminants. San Francisco, 21st Annual Conference on Mass Spectrometry and Allied Topics. May 1973. 48. Hammond, E. G. and R. G. Seals. Oxidized Flavor in Milk and Its Simulation. J. Dairy Sci. 5_5_:1567, 1972. 49. Ingram, S. H., R. C. Albin, C. D. Jones, A. M. Lennon, L. F. Tribble, L. B. Porter, and C. T. Gaskins. Swine Fecal Odor as Affected by Feed Additives. J. Ani. Sci. 3£:207, 1973. 50. Ingram, S. H., R. C. Albin, C. D. Jones, A. M. Lennon, L. F. Tribble, L. B. Porter, and C. T. Gaskins. Swine Fecal Odor as Affected by Feed Additives. Manuscript of Presentation (personal communication). 1973. 51. Anonymous. Sagebrush for Odor Control: In the Feed or the Manure? 14:74, 1972. 67 ------- 52. Amerine, M. A., R. M. Pangborn, and E. B. Poessler. Principles of Sensory Evaluation of Food. New York, Academic Press, 1965. 53. A.S.T.M. Manual on Sensory Testing Methods. American Society for Testing and Materials, Spec. Tech. Pub. 434, 1968. 54. A.S.T.M. Basic Principles of Sensory Evaluation. American Society for Testing and Materials, Spec. Tech. Pub. 433, 1968. 55. A.P.H.A. Standard Methods for the Examination of Water and Wastewater. American Public Health Associa- tion, 1970. 56. Hach. Hydrogen Sulfide - Methylene Blue Method. Ames, Hach Chemical Company, 1970. 57. Bremner, J. M. and D. R. Kenney. Steam Distillation Methods for Determination of Ammonium, Nitrate and Nitrite. Anal. Chem. ACTA, 32,:485, 1965. 58. Ekladius, L. and H. K. King. A Colormetric Method for the Determination of Aliphatic Amines in the Presence of Ammonia. Biochem. J. 6J5(1) :128, 1957. 59. Anonymous. Hycel Urea Nitrogen Determination. Houston, Hycel Inc., 1964. 68 ------- SECTION VIII LIST OF PUBLICATIONS 1. Miner, J. R. Odor from Livestock Production. Agri- cultural Engineering Department, Oregon State University. August 1973. 137 p. 2. Miner, J. R. Odors from Confined Livestock Production. Environmental Protection Technology Series, EPA-660/2- 74-023. April 1974. 125 p. 3. White, R. K. , C. L. Bart, D. C. Ludington, and J. R. Miner. Sampling and Analyses of Gases/Odors. In: Standardizing Properties and Analytical Methods Related to Animal Waste Research. Amer. Soc. Agr. Engr., Paper No. 74-4544. Special Pub. SP-0275, 1975. p. 282-296. 4. Miner, J. R. , M. D. Kelly, and A. W. Anderson. Identi- fication and Measurement of Volatile Compounds Within a Swine Confinement Building and Measurement of Ammonia Evolution Rates from Manure Covered Surfaces. In: Managing Livestock Wastes. Proceedings, 3rd Inter. Symp. on Livestock Wastes. ASAE Pub. PROC-275, 1975. p. 351-353. 5. Miner, J. R. Management of Odors Associated with Live- stock Production. In: Managing Livestock Wastes. Proceedings, 3rd Inter. Symp. on Livestock Wastes. ASAE Pub. PROC-275, 1975. p. 378-380. 6. Miner, J. R. Engineering Challenges of Animal Production Odor Control. Proceedings, AIChE-EPA "WateReuse" Con- ference, Chicago. May 4-8, 1975. (In press). 7. Miner, J. R. Management of Odors Associated with Live- stock Production. Proceedings, Michigan State University, Agricultural Waste Conference. April 1975. (In press). 69 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1 . REPORT NO. EPA-6QQ/2-76-239 3. RECIPIENT'S ACCESSION-NO. 4. TITLE AND SUBTITLE PRODUCTION AND TRANSPORT OF GASEOUS NH3 AND H2S ASSOCIATED WITH LIVESTOCK PRODUCTION 5. REPORT DATE September 1976 (Issue Date) 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) J. Ronald Miner 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS Agricultural Engineering Department Oregon State University Corvallis, Oregon 97331 10. PROGRAM ELEMENT NO. 1HB617 11. CONTRACT/GRANT NO. S-802009 12. SPONSORING AGENCY NAME AND ADDRESS Robert S. Kerr Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Ada, Oklahoma 74820 13. TYPE OF REPORT AND PERIOD COVERED Final Report (2/73-12/75) 14. SPONSORING AGENCY CODE EPA-ORD 15. SUPPLEMENTARY NOTES 16. ABSTRACT Current livestock production techniques release a large variety of volatile organic compounds to the atmosphere. This release results in complaints due to their odorous nature and has been identified as a source of surface water pollution as these compounds are absorbed from the air. Ammonia has been identified as the compound of greatest concern relative to water pollution and is of considerable interest relative to odor complaints due to its ease of measurement and its relationship to more odorous gas evolution. Gas sampling and measuring schemes based upon the use of solid absorbents were studied. Use of an absorbent suspended in a stainless steel screen container which could be exposed in an atmosphere to be sampled showed promise. The evolution of ammonia, hydrogen sulfide and odorous volatiles was investi- gated as a function of beef cattle ration. Addition of essential oil, mint oil, was found to mask the odor of fresh manure. Mint oil was carried in the urine. Ammonia evolution from fresh manure was largely from urine. Fecal contributions became significant only after significant decomposition had occurred. A technique was devised for measuring ammonia evolution rates from surfaces. This measurement proved an accurate measure of anaerobic biological activity and provided a quantitative means for comparing treatment procedures designed to minimize volatile material evolution rates. Evolution rates for a variety of surfaces associated with livestock production enterprises were measured. 7. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS COSATl Field/Group Cattle; Swine; Agricultural Wastes; Odors; Water Pollution Ammonia Volatilization Rate; Ration Effects; Ammonia Absorption; Gas Sampling; Feces; Urine 02/A, B, C 3. DISTRIBUTION STATEMENT RELEASE UNLIMITED 19. SECURITY CLASS (This Report) Unclassified 21. NO. OF PAGES 20. SECURITY CLASS (Thispage) Unclassified 22. PRICE EPA Form 2220-1 (9-73) 70 ft U.S. GOVERNMENT PRINTING OFFICE 1977- 757-056/5465 ------- |