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

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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

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 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

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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

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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

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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

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 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

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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

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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

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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

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 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

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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

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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

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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

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 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

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                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

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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.

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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.

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 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

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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

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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

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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

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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

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                     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

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 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

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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

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 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

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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.

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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

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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

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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

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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

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 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

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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

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                       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

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                          	 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

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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

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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

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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

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                  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

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 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

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AIR PUMP
                      MANURE
                        SLURRY
Figure  7.  Laboratory  apparatus used to evaluate the ability of
          various absorbing materials to remove ammonia from
          odorous air.
                            59

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 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

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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

                        REFERENCES
1.  Schlossing, T.  Determination of Atmospheric Ammonia.
    Compt. Rend.  80^:175-178,  265-268,  1875.

2.  Weatherby, J. H.  Chronic  Toxicity  of Ammonia Fumes
    by Inhalation.  Proceedings, Soc. Exptl. Biol., 1952.
    8_1:300.

3.  Anderson, D. P., R. R. Wolfe, F. L. Cherms, and W. E.
    Roper.  Influence of Dust  and Ammonia on the Develop-
    ment of Air Sac Lesions  in Turkeys.  Am. J. Vet. Res.
    2£:1049-1058, 1968.

4.  Charles, D. R. and C. G. Payne.  The Influence of
    Graded Levels of Atmospheric Ammonia on Chickens.
    British Poultry Sci., 7:177, 1966.

5.  Boyd, E. M., M. L. MacLachlan, and  W. F. Perry.  Ex-
    perimental Ammonia Gas Poisoning in Rabbits and Cats.
    J. Ind. Hyg. Toxicol.  2^:29, 1964.

6.  Hutchinson, G. L. and F. G. Viets,  Jr.  Nitrogen En-
    richment of Surface Water  by Absorption of Ammonia
    Volatilized from Cattle  Feedlots.   Science.  166:514,
    1969.

7.  Luebs, R. E., K. R. Davis, and A. E. Laag.  Enrichment
    of Atmosphere with Nitrogen Compounds Volatilized from
    a Large Dairy Area.  J.  Envir. Qual.  2_(~L) :137, 1973.

8.  McCalla, T. M. and F. G. Viets, Jr.  Proceedings,
    Pollution Research Symp.,  University of Nebraska,
    May 23, 1969.
                            63

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 9.  Stephens, E. R.  Identification of Odors in Feedlot
     Operations.  Environmental Protection Agency Publication
     SW-5r.2, 1971.  24 p.

10.  Miner, J. R. and T. E. Hazen.  Ammonia and Amines:
     Components of Swine-Building Atmosphere.  Trans. Amer.
     Soc. Agr. Engr.  12(6) : 772-774 , 1973.

11.  Ryan, J. A. and D. R. Kenney.  Ammonia Volatilization
     from Surface Applied Wastewater Sludge.  J. Water Poll.
     Control Fed.  1975.

12.  Koelliker, J. K. and J. R. Miner.  Desorption of Ammonia
     from Anaerobic Lagoons.  Trans. Amer. Soc. Agr. Engr.
     16_(1):148, 1973.

13.  Stewart, B. A.  Volatilization and Nitrification of
     Nitrogen from Urine Under Simulated Cattle Feedlot
     Conditions.  J. Envir. Sci. and Tech.  4_(7) :579-582,
     1970.

14.  Elliott, L. F., G. E. Schuman, and F. G. Viets, Jr.
     Volatilization of Nitrogen-Containing Compounds from
     Beef Cattle Areas.  In:  Proceedings, Soil Sci. Soc.
     Amer., 1971.  35_:752.

15.  Adriano, D. C., A. C. Chang, and R. Sharpless.  Nitrogen
     Loss from Manure as Influenced by Moisture and Tempera-
     ture.  J. Envir. Qual.  3^(3) :258, 1975.

16.  Ludington, D. C., A. T. Sobel, and A. G. Hashimoto.
     Odors and Gases Liberated from Diluted and Undiluted
     Chicken Manure.  Paper No. 69-426.  Amer. Soc. Agr.
     Engr.  1969.

17.  Luebs, R. E., K. R. Davis, and A. E. Laag.  Diurnal
     Fluctuation and Movement of Atmospheric Ammonia and
     Related Gases from Dairies.  J. Envir. Qual.  _3(3) :265,
     1974.

18.  Miner, J. R.  Odors from Confined Livestock Production.
     Environmental Protection Technology Series.  EPA-660/2-
     74-023, 1974.  125 p.

19.  Chao, T. and W. Kroontje.  The Relationships Between
     Ammonia Volatilization, Ammonia Concentration and Water
     Evaporation.  In:  Proceedings, Soil Sci. Soc. Amer.,
     1964.  28:393.
                             64

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20.  Viets, F. G., Jr.  Symposium on Agriculturally  Related
     Pollution and Fertilizer  Conference.  Bozeman,  February
     1970.  p. 11-16.

21.  Earth, C. L. and L. B.  Polkowski.   Identifying  Odorous
     Components on Stored  Dairy Manure.  Trans. Amer. Soc.
     Agr. Engr.  r?(4) : 737-740 , 1974.

22.  Merkel, J. A. , T. E.  Hazen, and J.  R. Miner.  Identi-
     fication of Gases in  a  Confinement  Swine Building
     Atmosphere.  Trans. Amer. Soc. Agr. Engr.  12 (3) .-310-315,
     1969.                                      —

23.  Leonardos, G. , D. A.  Kendall,  and N. J. Barnard.  Odor
     Threshold Determinations  of 53 Odorant Chemicals.  J.
     Air Poll. Control Assoc.  19_:91, 1969.

24.  White, R. K., E. P. Taiganides, and G. Cole.  Chromato-
     graphic Identification  of Malodors  from Dairy Animal
     Waste.  In:  Proceedings, Inter. Symp. of Livestock
     Wastes.  St. Joseph,  Amer. Soc. Agr. Engr., 1971.

25.  Luebs , R. E., A. E. Laag, and  K. R. Davis.  Ammonia and
     Related Gases Emanating from a Large Dairy Area.  Calif.
     Agr.  r7(2) :10, 1973.
26.  Burnett, W. E.  and N.  C.  Dondero.  Microbiological and
     Chemical Changes  in  Poultry Manure Associated with De-
     composition and Odor Generation.  In:  Proceedings,
     Cornell University,  Conf.  on Agr. Waste Mgmt., 1969.
     p. 271.

27.  Mosier, A. R.   Effect  of  Cattle Feedlot Volatiles,
     Aliphatic Amines, on Chlorella Ellipsoidea Growth.  J.
     Envir. Qual.   ,3(1):26-30,  1974.

28.  Day, D. L. , E.  L. Hansen,  and S. Anderson.  Gases and
     Odors in Confinement Swine Buildings.  Trans. Amer.
     Soc. Agr. Engr.   8^:118, 1965.

29.  Hammond, W. C. , D. L.  Day, and E. L. Hansen.  Can Lime
     and Chlorine Suppress  Odors in Liquid  Hog Manure.  Agr
     Engr.  4!?: 340,  1968.

30.  Curtis, S. E.   The Pig's  Air Environment in Enclosed
     Accommodations.   Feedstuffs.  £7(11),  March 1975.

31.  Taiganides, E.  P. and  R.  K. White.   The Menace of
     Noxious Gases  in  Animal Units.  Trans. Amer.  Soc. Agr.
     Engr.  12:359,  1969.
                             65

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 32.  Burnett, W. E.  Air Pollution  from Animal Wastes-
     Determination of Malodors by Gas  Chromatographic and
     Organoleptic Techniques.  Envir.  Sci.  Tech., ^3:744,
     August  1969.

 33.  Bethea, R. M. and  R. S. Narayan.  Identification of
     Beef Cattle Feedlot Odors.  Trans. Amer. Soc. Agr. Engr.
     15:1135, 1972.

 34.  Avery,  G. L., G. E. Merva,  and J. B. Gerrish.  Hydrogen
     Sulfide Production in Swine Confinement Units.  Trans.
     Amer. Soc. Agr. Engr.  1JJ(1) :149, 1975.

 35.  Burnett, W. E. and A. T. Sob«l.   Odors, Gases, and
     Particulate Matter from High Density Poultry Manage-
     ment Systems as They Relate to Air Pollution.  Depart-
     ments of Food Science and Agricultural Engineering,
     Ithaca, N.Y.  Progress Report  No. 1, N.Y. State Con-
     tract No. 1101.  1967.

 36.  Merkel, J. A.  Atmospheric  Composition in an Enclosed
     Swine Production Building.  Unpublished Ph.D. thesis,
     Ames, Iowa State University Library, 1967,

 37.  Frus, J. D., T. E. Hazen, and  J.  R. Miner.  Chemical
     Oxygen Demand of Gaseous Air Contaminants.  Trans.
     Amer. Soc. Agr. Engr.  1£(5) :837, 1971.

 38.  Mosier, A. R., C.  W. Andie, and F. G.  Viets, Jr.
     Identification of  Aliphatic Amines Volatiles from
     Cattle Feedyard.   J. Envir. Sci.  and Tech.  7^(7) :642-
     644, 1973.

 39.  Day, E. A., D. A.  Forss, and S. Patton.  Identification
     of Volatile Components by Gas  Chromatography and Mass
     Spectrometry.  J.  Dairy Sci.   £1:932,  1958.

40.  Rasmussen, R. A.   Analysis  of  Trace Organic Sulfur
     Compounds to Air.  American Laboratory,  p. 55-61,
     December 1972.

41.  Zlatkis, A., H. A. Lichtenstein,  A. Tishbee, W. Bertsch,
     F. Shunbo, and H.  M. Liebich.  Concentration and Analy-
     sis of Volatile Urinary Metabolites.   J. Chromatographic
     Sci.  11:299-302,  1973.
                             66

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42.  Miller, A., Ill, R. A. Scanlan, J. S. Lee, and L. M.
     Libbey.  Volatile Compounds Produced in Sterile Fish
     Muscle (Sebastes melanops) by Pseudomonas putrefaciens,
     Pseudomonas fluorescens,  and an Achromobacter Species.
     Applied Micro,  p. 18-21, July 1973.

43.  Rudinsky, J. A., M. Morgan, L. M. Libbey, and R. R.
     Michael.  Sound Production in Scolytidae;  3-methyl-
     2-cyclohexene-l-one Released by the Female Douglas
     Fir Beetle in Response to Male Sonic Signal.  Environ-
     mental Entomology.  2_(4) , August  1973.

44.  Hartung, L. D. , E. G. Hammond, and J. R. Miner.  Iden-
     tification of Carbonyl Compounds  in a Swine-Building
     Atmosphere.  In:  Proceedings, Inter. Symp- of Live-
     stock Wastes.  Amer. Soc. Agr. Engr., Pub. SP-271.
     1971.  p. 105-107.

45.  Suffis, R. and D. E. Dean.  Identification of Alcoholic
     Peaks in Gas Chromatography by a  Non-Aqueous Extraction
     Technique.  Anal. Chem.   3£:480-483, 1972.

46.  Hammond, E. G. , G. A. Junk, P. Kuczala, and J. Kozel.
     Constituents of Swine House Odors.  In:  Proceedings,
     Inter. Livestock Envir.  Symp.  Amer. Soc. Agr. Engr.,
     SP 01-74.  1974.  p. 364-372.

47.  Junk, G. A. and H. J. Svec.  The  Use of Macroreticular
     Resins in the Analysis of Water for Trace Organic Con-
     taminants.  San Francisco, 21st Annual Conference on
     Mass Spectrometry and Allied Topics.  May 1973.

48.  Hammond, E. G. and R. G.  Seals.   Oxidized Flavor in
     Milk and Its Simulation.  J. Dairy Sci.  5_5_:1567, 1972.

49.  Ingram, S. H., R. C. Albin, C. D. Jones, A. M. Lennon,
     L. F. Tribble, L. B. Porter, and  C. T. Gaskins.  Swine
     Fecal Odor as Affected by Feed Additives.  J. Ani. Sci.
     3£:207, 1973.

50.  Ingram, S. H., R. C. Albin, C. D. Jones, A. M. Lennon,
     L. F. Tribble, L. B. Porter, and  C. T. Gaskins.  Swine
     Fecal Odor as Affected by Feed Additives.  Manuscript
     of Presentation  (personal communication).  1973.

51.  Anonymous.  Sagebrush for Odor Control:  In the Feed
     or the Manure?  14:74, 1972.
                             67

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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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