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
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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.
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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
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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.
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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
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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
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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
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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
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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
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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
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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
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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
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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 .
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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.
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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.
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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
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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.
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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
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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.
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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.
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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.
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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
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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
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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
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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
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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
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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
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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
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SECTION VII
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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
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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
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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
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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
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