CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

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^^<. CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT WASTE by ANGEL ALBERTO AGUILAR A THESIS IN ANIMAL SCIENCE Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE Approved May, 1975

Transcript of CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

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^^<.

CONTROL OF VOLATILE COMPOUNDS

IN CATTLE FEEDLOT WASTE

by

ANGEL ALBERTO AGUILAR

A THESIS

IN

ANIMAL SCIENCE

Submitted to the Graduate Faculty of Texas Tech University in

Partial Fulfillment of the Requirements for

the Degree of

MASTER OF SCIENCE

Approved

May, 1975

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/ I

73 1^7^ ACKNOWLEDGMENTS

AJo. 3 ^if> 2. y sincere appreciation is extended to Dr. Robert C.

Albin for his assistance and guidance throughout the preparation

of this manuscript and to Dr. Daniel R. Krieg and Mrs. Lucy

Porter for their aid during the collection of data.

Gratitude is also extended to Dr. Leif H. Thompson for

his advice, and to U.S. Gypsum Company for supplying the gypsum

and partial funding for this study.

This manuscript is dedicated to my parents, Dr. Angel

Aguilar and Maria Teresa Aguilar, whose love and sacrifices

made it possible.

n

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TABLE OF CONTENTS

ACKT^OWLEDGMENTS IT

LIST OF TABLES iv

I. INTRODUCTION 1

II. LITERATURE REVIEW 3

III. EXPERIMENTAL PROCEDURE 25

IV. RESULTS AND DISCUSSION 32

V. SUMMARY AND CONCLUSIONS 38

LITERATURE CITED 40

APPENDIX. 46

m

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LIST OF TABLES

TABLE NUMBER

1. Least Squares Means for Parameters Measured

at the Pantex and Lubbock Feedlot Locations 34

2. Mean Squares from the Analysis of Variance 35

3. Gas Chromatography Data for Lubbock Feedlot Column A: Acids and Aldehydes 47

4. Gas Chromatography Data for Lubbock Feedlot Column B: Amines 43

5. Gas Chromatography Data for Pantex Column A: Acids & Aldehydes 49

6. Gas Chromatography Data for Pantex

Column B: Amines 50

7. Matching Standards Method Data Sheet 52

8. Odor Panel Recording Sheet 53

IV

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INTRODUCTION

Cattle feedlots undoubtedly antedate written history.

Probably, the first feedlot was established shortly after cattle

were first domesticated. Cattle feedlots are among the more

important operations in American agriculture today. Cattl-j

and calf sales gross more cash than the combined sales of cotton,

corn, wheat, peanuts, tobacco and rice (U.S.D.A., 1972). Cattle

feedlot operations are an especially important industry on the Texas f

High Plains. Total current feeding capacity in this area is over

2,000,000 head.j

The trend toward concentrated cattle feeding started

shortly after World War II. It took until the mid 1950's for

the trend of concentrated animal production to develop to the point

that an awareness of the pollution potential of animal wastes was

recognized. Even then, there was no measure of the magnitude of

the problem. It wasn't until the early 1960's that these data

were developed, but even then the data related mostly to water

pollution (Hazen, 1972).

Air pollution was a different matter. Baseline data

were not available. This was particularily true in the case of

odors. Odor perception is highly subjective and variable. The

biological system producing odors by decomposing manure is highly

variable and extremely complex. Active work to isolate, identify

and measure components of manure odor has been going on since

1

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the early 1960's. Identification of some odorous components

was rapid. One of the early reports on these components v/as

by Day et_ aj,. (1965).

Odors from animal wastes are a persistent problem

arising from the confinement of large numbers of animals. The

problem is especially prevalent near feedlots, in and around

confined and enclosed animal production operations, and where

field spreading of unestablished waste from confinement operations

is practiced. There is an acute need for effective methods of

odor control if agricultural industries are to co-exist with

their neighbors. Effective odor control must be based on an

understanding of the fundamentals of odor generation and control

and on a knowledge of the odor causing compound (Loehr, 1974b).

The objective of this project was to determine the

effect of adding gypsum to waste accumulations on feedlot surfaces

and stockpiled waste with respect to volatile compounds in the cattle

feedlot waste.

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LITERATURE REVIEW

I. CHARACTERIZATION OF ANIMAL WASTE ODORS

Llllie (1970) published a literature survey concerning the

effects of many air pollutants on domestic animals. The effects

of hydrogen sulfide, ammonia, carbon monoxide and some hydrocarbons

are of particular interest since they are known decomposition

products of animal wastes under some conditions. Seltzer et al.

(1969) cited several cases of the adverse effects of ammonia and

other manure gases on poultry and other animals.

There is no location to which the feedlot operator can move

to escape this phenomenon. It is, however, apparent that environ­

mental pollution will not be acceptable in any animal production

area in the future. Odors are the most frequent complaint directed

at animal production in the near urban location. At the present

time, it appears that the primary basis for regulating odors from

animal production is to eliminate an unacceptable nuisance. It is

suggested in a large quantity of literature that many odorants from

the decomposition of animal excreta are not physically harmful at

levels which are psychologically intolerable (Hazen, 1972). Actual

physiological damage to neighbors from animal waste odors has not

been proven in court; however, nuisance and property damage have

been proven (Miner, 1970b; Feedlot Operators, 1972; Willrich and

Miner, 1971).

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At least ninteen states have regulations defining odor as

an environmental pollutant. Similar regulations are under consid­

eration in five other states. Nine of the nineteen employ qualitative

standards, while nine employ quantitative standards, and only three

employ both in their regulations. Quantitative measurerr.ent is

usually by odormeter and qualitative is by inspections, panels, end

random sampling (Barth, 1970a). While the Environmental Protection

Agency has given no recommended limits for odorous emissions, the

Texas Air Control Board is considering issuing standards for odorous

emissions within a year (Sweeten, 1973).

Confined feeding has raised certain questions regarding the

feasibility of land disposal of manures in some areas. Where large

quantities of wastes are generated in concentrated areas, the logis­

tics of land disposal in the traditional sense sometimes present

formidable problems. Direct land disposal of manures from large

livestock enterprises located in areas of dense population often

becomes a nuisance because of flies and odor.

The excreta in a feedlot is a source of considerable atmo­

spheric odor. In a commercial feedlot, the average 1,000 pound steer

will produce 85 pounds total excreta each day, of which 30 pounds is

urine. When wet this excreta produces more offensive gases and odors

and disagreeable and irritative dust particles than when dry

(Narayan, 1971).

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In confined livestock buildings, the existing gases become

objectionable for the working personnel. Certainly not the least of

these problems is the nuisance effect of the cattle feedlot odors with

regard to operators and neighbors, both adjacent and downwind. It

is interesting to note that even large firms, such as the Monfort

feedlots in Greeley, Colorado, and the Roy F. Benton feedyard in

Pomona, California, have been sued for damages or prosecuted as

public nuisances because of the feedlot odors and have been forced

to institute odor control programs (Narayan, 1971; Russel, 1965).

Many different methods have been used in attempts to

characterize the odorous components of animal manure decomposition.

There are certain characteristics of odors which are known. An

odor is an effect, the result of the stimulation of an individual's

olfactory region. Odorants and odorous substances are the materials

producing the stimulus (Yocom, 1970). Significant observations based

on laboratory studies were that odor production increases with

increasing manure volume, but not linearly; that diluted manure

has a higher odor strength then undiluted manure; that mixed manure

has a stronger smell than unmixed; that mixing releases odors

promptly; and that maximum odor production occurs between two and seven

days for batch samples (Sobel, 1969a). Only substances which are

volatile are odorous, however, many volatile substances do not

have odors. Substances having the same chemical composition (isomers)

have wery different odors. Substances having wery different

chemical compositions may have similar odors. Some

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odorous substances must have a concentration of a million times

greater than others in order to be detected by smell. Variation

In the concentration of an odorant may cause a change in the

quality of the odor. Air movement must take place in the nasal

cavity for odors to be perceived (Barth, 1970b).

In a feedlot, we are dealing with perhaps thousands of

chemical compounds In feces that come from feeds, animal metabolism,

and microbial by-products produced either in the animal or by

putrefaction on the feedlot surface. Little is known about these

compounds or their environmental significance. Among them are large

quantities of urea, which quickly hydrolyzes to ammonia, and volatile

amines, skatole, indole, sulfur compounds, and organic acids that

have bad odors (Viets, 1971).

Animals in confinement are fed rations of a composition to

cause the greatest weight gain in the shortest time, which includes

a greater proportion of grain than roughage. Highly efficient

utilization of the feed by the animal is requisite to continuous and

rapid weight gain by the animal. Wastes produced under these circum­

stances will contain more material capable of causing nuisance and

pollutional problems than will waste produced under conditions where

weight gain Is less critical. Animals of the same kind that are fed

more concentrates excrete more of the nutritive material because the

food contains more (Jones, et_ aj_. undated; Loehr, 1968a; Loehr, 1974b)

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Components of livestock wastes important to biological

treatment (Jones et a K , undated).

LIVESTOCK MANURE (Organic Matter)

Dry Matter (solids)

/

Volatile (organic) /

Biodegradable

Water

Non Volatile (inorganic, fixed, ash)

Nonbiodegradable

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The principal agents of pollution arising from animal

manures are organic substances. Both biodegradable and relatively

unbiodegradable; inorganic substances and volatile substances, which

may aesthetically degrade our air and water. The organic matter,

upon reaching a body of receiving water, serves as substrate for

growth of aerobic-microorganisms, which can rapidly deplete the

available dissolved oxygen. Anaerobic microorganisms, also produce

a variety of noxious end-products (Miner, 1970b).

Classification of the physical, chemical, and biological

characteristics of body excreta from feeder cattle is essential

to the establishment of control, treatment, and disposal methods.

Considerable variation exists in the excreta from these animals.

This variation is affected by animal size, climatic variation, and

type of ration which the animals are fed. Fresh manure ranges

from 80 to 85 percent moisture, it contains undigested food from

the digestive tract, unabsorbed digestive juices, cells and mucuous

from the digestive tract, microorganisms, and waste minerals such

as calcium, magnesium, iron and phosphorus. Most of these materials

are readily degraded by microorganisms when they are exposed to

favorable environmental conditions (Grub et al_.» 1968).

We have long known that the cardinal principle on which all

waste treatment.is based is to provide an environment in which the

microorganisms can bring about conversion of undesirable material

to an inoffensive and stable state in the shortest possible time.

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To bring about this desired condition it is necessary to

consider the following:

A. the waste we want to treat and,

B. the organisms that we want to perform this core for us.

To reduce a particular material by specific microorganis.-s necessitates

the proper environment. The biochemical reactions of anaerobic bac­

teria are quite different from an aerobe. The kind of oxygen, whether

it be free or chemically combined, is important. The microorganisms

involved in manure reduction are within the following groups:

A. Bacteria (eerobic, anaerobic, microaerophilic, facultative or obligate)

B. Fungi

C. Actinomycete

D. Protozoa

E. Algae

F. Bacteriophage

The nature and condition of the waste material does much to

select the types of microorganisms that predominate. Carbohydrates

stimulate both the bacteria and fungi. Carbohydrates may be reduced

through bacterial degradation to organic acids, aldehydes, ketones,

and alcohols. Inorganic solutions rich in nitrates stimulate a

growth of algae, and abundance of algae and bacteria is favorable

for the growth of the protozoa. The anaerobic degradation of

proteins is brought about by the facultative anaerobic and obligate

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anaerobic bacteria. The end-products of their metabolism are skatol,

mercaptans, tjtyric acids, the reduction of the sulfates to HpS,

and aldehydes (Miner, 1969a; Loehr, 1974b).

Waste removed from beef cattle feedlots will have character­

istics different than fresh manure. The characteristics change as

the manure undergoes drying, microbial action, wetting by precipita­

tion, and mixing and compaction by animal movement. Beef wastes

average 80-85% volatile matter (Loehr, 1974b).

Only substances having the form of fine mists, gases or

vapors can be smelled. Odors can, however, be associated with

solid particulate matter. Burnett (1969a) collected particulate

matter from a poultry laying house. A panel of at least eight people

determined that the dust carried a "chicken house" odor. The odors

dissipated after standing for at least 12 hours at room temperature

or being dried at 100°C, thereby indicating that they were due to

one or more volatile compounds. When these vol atlies were subjected

to chromatographic analysis coupled with organoleptic evaluation,

a number of compounds had strong odors. Since no individual compound

had the typical "chicken house" odor, the assumption was made that

the typical odor was a blend of several odorous materials.

In spite of the sophisticated technical equipment that has

been developed, .the human odor sensing system remains the most suitable

detector available. Most odors are a complex mixture of chemical

compounds. In some odors a specific compound such as ammonia or

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hydrogen sulfide can be predominant and detected instrumentally to

obtain a measure of its strength. Because most odors are caused

by small amounts of a number of compounds, a human odor panel remains

one of the best odor detection and evaluation systems (Amer. Soc.

Test. Mat., 1968).

Methane, while odorless, has negligible solubility in water

at ordinary pressures and escapes immediately upon production.

The pH affects the solubility of many compounds. Under conditions

of high pH, hydrogen sulfide is mostly dissociated and present as

H and HS" ions, resulting in few detectable odors. If the pH

is lowered, ionization decreases and the odor of hydrogen sulfide

is readily detected.

Odor intensities may be expressed in several ways. Typical

are the threshold odor number (TON) and the odor intensity index

( o n ) . The following equation relates the two values:

TON = 2* ^

The number of times an odorant must be diluted by half with

an odorless agent until the odor is just detectable (threshold)

is the Odor Intensity Index. The greatest dilution of an odorant

with an odorless agent until the odor is just detectable is the

Threshold Odor Number (Barth, 1970b, 1971c, 1972d).

A Threshold Odor Number of one means that an air sample is

odorless. Threshold odor is an attempt to quantify the least amount

of a substance to produce an odor that can be detected under a

specific set of conditions, including that of the tester. This

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definition Is based on four known facts as follows:

1. a weak odor will not be noticed in the presence of a strong odor;

2. an unrecognizable odor will be produced by the blending of two odors of equal strengths;

3. awareness of an odor will be diminished by constant contact; and

4. the like or dislike of an odor is affected by past experience (Santry, 1966).

Odormeters have been developed which assist in odor measure­

ment. These instruments have taken various forms, but all make

the necessary dilutions of odorous air with odor free air before

inhalation (Sweeten, 1973). Osometer, odormeter, osmoscope, scento-

meter, olfactometer, and olfactoscope are some of the names which

have been given these instruments.

Liquid dilution can be used to measure the odor strength

of manures and dilution with odor free air can be used to measure

the strength of the released gases (Ludington et_ al_., 1969d).

According to Sobel (1970b), the offensiveness of the odor appears

to be proportional to the logarithm of the moisture content in the

measurement of odors from animal manures.

A wery important apparatus in odor research has been the

gas chromatograph. The gas chromatograph can best separate and

quantify odorants while the human nose can best determine the quality

and Intensity of simple and complex combinations of odorants. The

capabilities of one compliments the other rather than one supolimpntina

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the other (Stephens, 1974; Barth, 1970b). Bentsen and Bethea (1969)

gave a description of a computer program which will aid in the

qualitative and quantitative analysis of unknown samples by gas

chromatography.

II. ODOR CONTROL

With the passage of the Federal Air Quality Act of 1357,

there remains little doubt that the emmission of odorous effluents

will have to be abated. Current technology has given us a large

quantity of equipment, chemicals, and other products from v/hich to

choose in the development of odor control systems (Ulich, 1974). The

following literature review provides a survey of many attempts, both

successful and unsuccessful, at odor abatement in commercial livestock

and poultry operations.

Chlorine

Hedrich (1935) stated that atmospheric oxidation of malodors

with chlorine was unsuccessful. According to Santry (1966) chlorine

has been used for the control of hydrogen sulfide in sewers. Chlorine

was quite expensive for this purpose. Deibel (1967) tested sodium

chloride in concentrations as strong as eight percent without total

loss of odor in poultry manure. Chlorination is one method of

hydrogen sulfide control in common use. The following equation

describes one reaction of hydrogen sulfide and chlorine:

H^S + Clo > 2 HCL + S

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The theoretical quantity of chlorine to react with a pound of

hydrogen sulfide for this reaction is 2.1 pounds; however, excess

chloride must be present for this reaction to occur. When excess

chloride is present, another reaction also takes place.

H2S + 4 CI2 + 4 H2O > H2S0^ + 8 HCL

Ozonation

Deibel (1967) reported that direct ozonation of poultry manure

was unsuccessful in abating odors. Baugh and Burchard (1972) described

the use of ozone in treating toxic and strong smelling liquid ef­

fluents. The use of ozone reduced oxygen demand, but not all organic

materials were oxidized. A striking reduction of odors occurred.

Nakano (1972) reported that ozonation was used successfully for the

treatment of sewage digestion odors in Nagoya, Japan. Okuno (1972)

discussed the mechanism by which ozone destroys sulfurous compounds,

lower molecular amines, and acids. Reactivity was determined by

measuring the quantity of residual ozone and monitoring the reaction

products by gas chromatography. Not all odorous components can,

however, be removed by ozone oxidation. Some odorous substances were

found to react faster than others. Baba (1971) gave information on

using ozonation as a control technique for odors from human sewage.

Comparative cost data were presented for thermal and catalytic

Incineration, absorption, chlorination, and ozonation. Ozonation

was shown to be the least expensive. Elliot (1971) stated that

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ozonation was most effective in the reduction of organic odorants.

Dosage requirements depended upon retention time, humidity, and

temperature.

Orthodi chlorobenzene

Orthodichlorobenzene was used for hydrogen su'fidf ' control

with good results at dosages as low as 1.5 parts per million. The

Los Angeles County Sanitation district found that 40 parts per

million was necessary to reduce the hydrogen sulfide generation by

50%; however, a poor point of application was used. It was noted

that orthodichlorobenzene exhibited a remarkable ability to mask

other odors (Pomroy, 1946). Deibel (1967) found that chloramine-T,

at a concentration of 50 p.p.m., deodorized liquid poultry manure

in ten minutes; however, it was effective for only about 24 hours.

The spraying of 300 gallons per acre of a 1% solution of Ozene, the

brand name of a formulation of orthodichlorobenzene, was recommended

for the control of feedlot odors. It was also recommended that the

lot be empty when sprayed, the feed not be contaminated, and the

spraying be repeated at regular intervals (Allied, Chem. Co., undated)

Lime

Yushok and Bear (1948) reported that odors from solid

poultry manure were greatly reduced when quicklime was used as a

preservative. Because of difficulty in the handling of quicklime,

the decision was made to compare its effects with that of hydrated

lime. Similar drying and deodorizing effects were observed for

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both products. The primary effect of either product was to slow the

decomposition rate of the manure. A bactericidal effect was noted.

Lime and chlorine have been used to suppress odors in hog wastes and

to provide some degree of treatment. About 0.15 pound of lime per

100 pound hog per day was required to maintain the pH at 10.00.

Over a six-month period, this amounted to $0.62 per hog. The chlorine

demand of the wastes was about 0.1 pound active for a six-month

period. About half this concentration would suppress odors.

Santry (1966) reported that a lime slurry had given good

control of hydrogen sulfide in sewers in Los Angeles County, California

Deibel (1967) found that lime added to liquid poultry manure initially

decreased both odors and bacterial growth. Hammond et al_. (1968)

studied the use of lime in suppressing odors from hog manure. Hydrated

lime was added to the manure at rates of 0.154 and 0.158 pounds per

day. This maintained the pH at nine or above. Hydrogen sulfide and

carbon dioxide production were reduced, but methane and ammonia

production were not appreciably changed by the addition of lime.

Potassium Permanganate

Faith (1970) reported that potassium permanganate gave

satisfactory results in the control of feedlot odors, provided that

good sanitation was maintained. Good housekeeping, including frequent

manure removal and scarification of the manure pack go provide aerobic

conditions, had not reduced odors to a satisfactory level at a

feedlot in Southern California. Various chemicals were tested in an

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attempt to further reduce odors. Potassium permanganate, applied

in a dilute water solution, was found to be most effective. A one

percent solution, was found to be most effective. A one percent

solution was sprayed in order to apply potassium permanganate in

amounts of twenty pounds per acre. Jedele and Andrew (1572) reported

that fifty thousand gallons of liquid manure were rendered odorless

by the use of potassium permanganate. The reported cost was nearly

as much as that needed to provide continuous operation of an oxidation

rotor.

Posselt and Reidies (1965) investigated potassium permanganate

solutions to determine their effectiveness in the destruction of

odors caused by a number of organic and inorganic compounds. Potassium

permanganate was shown to be effective for the abatement of esters,

mercaptans, phenol, and its derivatives, thioacids, and amines. Where

odor intensities were not reduced, often the characteristics were

changed from sickening to tolerable or even pleasant smelling. Some

gases, including ammonia, had a wery slow reaction with the solution.

Sodium Hydroxide

Benham (1967) reported that objectionable odors were

prevented for 28 days by the addition of sodium hydroxide to a two

to one mixture of water and poultry manure. The final concentration

was 0.9% NaOH by weight. Total aerobic bacteria and coliforms

were reduced in numbers.

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Phosphoric Acid

LaSalle and Launder (1969) reported that poultry manure

was Immediately deodorized, denatured, and stabilized upon intro­

duction into a weak solution of phosphoric acid. The dilute acid

solution was maintained at a pH of 3.5 to 4.0.

Hydrogen Peroxide

Laboratory tests have shown that hydrogen peroxide eliminates

atmospheric and sewage hydrogen sulfide at near stoichiometric

levels. Field tests were conducted in various parts of the country

with the same results. At pH's near neutral, hydrogen peroxide

reacts with hydrogen sulfide according to the following formula:

H2O2 + H2S > 2 H2O + S (Satterfleld et_ al_., 1954).

There are also indications that hydrogen peroxide acts as

a selective bacteriacide in the case of sulfate reducing bacteria

(F.M.C. Corp., undated).

Nitrates

McKinney and Conway (1957) used laboratory reactors to treat

socium acetate and an industrial waste substrate using nitrates as

a source of oxygen. Analysis for ammonia, nitrites, nitrates, and

dissolved oxygen showed that the nitrates were completely reduced

to nitrogen gas. This reduction took place without any buildup

of ammonia, nitrites, or dissolved oxygen. It was shown that of

the oxygen atoms available in the nitrate molecule, 2.5 were available

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for the oxidation of organic matter. There were no odors generated

by the nitrate-fed reactor. Hydrogen sulfide in sewers had been

controlled wich zinc sulfate and socium nitrate, but the cost has

generally been prohibitive (McKinney and Conway, 1957).

Digestive Deodorants

Digestive deodorants consist of a combination of digestive

enzymes, aerobic and anaerobic bacteria. The logic appears to be

that the enzymes or bacteria will create a digestive process

that eliminates the odor (Paine, undated).

Deibel (1967) tested several digestive deodorants and

found them to be ineffective in odor reduction. Of the forty-four

formulations of odor control agents tested by Burnett and Dondero

(1970b), the two digestive deodorants were found to be the

least effective. Ludington and Sobel (1969) reported that of the

forty commercially available odor control products evaluated, diges­

tive treatments, i.e., bacterial and enzyme starter cultures, were

the least effective.

Masking and Counteracting

Wright (1963) discussed masking and counteracting as two

of five methods proven for the control of odors. Masking agents are

mixtures of aeromatic oils which cover over the odor manure with

a stronger more "pleasant" odor. Note that the masking agent does

not reduce the smell. People have different preferences. Even if

this product is effective (i.e., it covers the manure odor) there

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may still be objections (Paine, undated). Certain factors of

Importance in the selection of masking agents are that they persist

under conditions of use, can be used with moderate strength, and

do not cause odor fatigue. The last item was especially important

since the loss of perception of one odor will not necessarily result

in the loss of perception of the odor being masked. Counteraction

in the antagonistic reaction of two or more odorants with the

olfactory sensory system causing a reduction in the intensity of

both. Potentially toxic compounds should not be treated with masking

or counteracting agents since the chemical makeup of the offensive

agent is not changed.

There are certain pairs of odors, which appear to cancel each

other when mixed in the correct relative concentrations. When the

two are sniffed together, the Intensity of each odor is diminished.

Certain mixtures of aeromatic oils (counteractants) are used to

neutralize the odor of manure. The true neutralization or counter­

action of odors leaves no overriding odor, pleasant or unpleasant

(Paine, undated). Moorman (1965) stated that odor counteraction

from air or ground spraying gave additional control where housekeep­

ing has not been successful in eliminating odor problems. Satisfactory

control of odors from feeding pens, storage sites, and during manure

handling had usually been attained by counteractant systems.

Deodorants are another type of odor control agent. A

deodorant is a mixture of chemicals designed to "kill" the odor

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of the manure. A deoderant usually does not use another "cover"

odor. The deodorant action may also kill the bacteria which

produces the odor (Paine, undated). Burnett and Dondero (1970b)

found that good control of odors from liquid poultry manure was

obtained by the use of commercial masking agents. Forty-four

formulations of masking agents, counteractants, and deodorants were

laboratory tested and rated according to their effectiveness in

controlling odors. Masking agents were found to be most effective

in control, with counteractants second, and deodorants least effective

Field tests were carried out using the masking agent judged most

effective in laboratory tests. Good odor control was attained during

spreading. Costs were estimated to be $0.63 per 450 gallons of liquid

manure.

Ludington and Sobel (1969b) reported that forty commercially

available odor control products were evaluated by an organoleptic

test for the control of odors from liquid manure. No completely

satisfactory odor control product was found. Deodorants were

moderately effective. The most effective were found to be masking

agents and counteractants.

Aeration

The lack of oxygen causes feedlot odor. Cattle manure still

contains energy for metabolism; microorganisms in the manure

accomplish this metabolism. When oxygen is present, the end-products

of metabolism are heat, CO2, and H2O. The oxygen transfer rate

Page 26: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

22

Into manure must exceed the demand to prevent odor (Paine, undated).

Ludington (1968a, 1969b, 1971c) studies odor production and

degradation of poultry manure with no aeration and excess aeration.

The use of ORP (Oxidation-Reduction Potential), for control purposes

allowed continuous monitoring of conditions from anaerobic to

aerobic. Monitoring of ORP could also readily be incorporated into

an automatic system to control aeration. Chicken manure was stored

at ORP's of 0, -150, -300, -400 millivolts, and with no aeration.

Manure stored with aeration produced no hydrogen sulfide, while that

stored with no aeration produced hydrogen sulfide.

The production of the six principal odorants identified by

White ejt a}^. (1971) were either diminished or eliminated by aeration.

The odorants were also diminished or eliminated when the electrode

potential was raised by direct electrical current being imposed on

the waste. Increasing the pH also reduced odors, but not to as

great an extent as raising the electrode potential or aeration

(Cooper et_ al., 1969).

According to Converse, et al_. (1971), a relatively odorless

condition, compared to anaerobic digestion, can be attained in

liquid hog manure utilizing aeration, but without maintaining a

dissolved oxygen residual. Aeration must be used to maintain the

oxidation-reduction potential (E cal) between -300 and -340 milli­

volts and the pH between 7.7 and 8.5. The average air flow required

to maintain these conditions was 216 cubic feet per pound of five day

Page 27: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

23

BOD (Biochemical Oxygen Demand).

Ration Modification

Nakano (1968) found that incorporation of 0.1% to 0.2%

by weight of humic acid into chicken feed rendered the manure odor­

less. Odors were substantially reduced in ten days and virtually

eliminated in twenty days. Thirty days were required to obtain

similar results with dogs. Both Bethea (1972) and Scarlet (1972)

discussed the possibility of humic acid being added to the feed

ration to prevent odors from cattle feedlots. Studies at Colorado

State University indicate that the inclusion of a small amount of

chopped sagebrush in feedlot rations eliminated or reduced odors.

Ground sagebrush was added to the rations of three groups of steers

at the rates of 0, 1, and 2 pounds per day. No significant difference

in feed efficiency was noted. The oils from the sagebrush acted as

a bactericide or a bacteriostat on the odor-producing organisms in

the animal's digestive tract (Anon, 1972).

According to Anthony (1969), the refeeding of fecal matter

gave the feedlot operator an economic incentive to clean the lot

each day. This recycling of unutilized feed material reduced feed

costs. In addition, water pollution from feedlot runoff was

decreased and odor problems were reduced.

Paraformaldehyde

Seltzer et_ aX. (1969) experimented with the effect of

paraformaldehyde on chicken feces. The paraformaldehyde prevented

Page 28: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

24

the build up of ammonia gas for twenty-eight days. The formaldehyde

gas which was released also acted as an anti-microbial agent.

Manures treated with ten percent paraformaldehyde retained

approximately double the nitrogen and ten times the amount of

sulfur as untreated manures. In another test, flies did not

deposit eggs in paraformaldehyde treated manure while doing so

in untreated control manure.

Gypsum

In soils with a gypsum content 40% could not be utilized

in agriculture without special reclamation. Effective reclamation

of such soils may be achieved by introducing high amounts of organic

matter, e.g., manure or perennial legume grass residues. A very

low respiration was observed in soils containing 70% gypsum

(3.45 mg CO2/2 Hr/110 cm ); the respiration rate was more than

doubled at a 30% gypsum content and was almost 4-fold as high at

a soil gypsum content of 4%. With increasing gypsum content, the

microbial count, ammonium' and nitrate N accumulation, and cellulose

decomposition decreased sharply (Ilovaiskaya ei al_., 1972).

Page 29: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

EXPERIMENTAL PROCEDURE

Gypsum applications were made at two feedlot locations,

one near Amarillo. Texas, in the Texas Tech University Center

at Pantex, and one in Lubbock, Texas, at Lubbock Feedlots to

see the effects of gypsum under commercial feedlot conditions.

Gypsum of two particle sizes (coarse = 1,800 - 2,200 cm^/gm

and fine = 20,000 cm'^/gm, surface area/gm of material) was added

to waste accumulations on the feedlot surfaces at 10%, 20%,

or 30% of the estimated dry matter accumulation. The pens and

fencelines were cleaned prior to initiation of the study and

after each finishing period. The two feedlot site investigations

were conducted over a period of nine months involving two

consecutive feeding periods with forty feedlot pens and approxi­

mately 1,200 head of cattle per period. There were thirty-tv;o dirt

surfaced pens at Pantex containing feeder cattle, twelve controls,

ten coarse gypsum and ten fine gypsum. At Lubbock Feedlots,

there were eight concrete surfaced pens; two controls, two coarse

gypsum, two fine gypsum, and two chemical spray. The gypsum was

spread on the surface of the cattle manure once a week. Every

three weeks, a core sample was taken from five locations per

pen, and analyzed that same day by the panelists.

In addition to the field studies, a series of experiments

were conducted in the Animal Science Research Laboratory on campus.

25

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26

using samples of fresh manure taken once a week to determine the

effects of different levels of moisture and gypsum upon volatile

compounds in the manure. All the samples were analyzed by an

olfactory panel for qualitative characteristics, and for

quantitative characteristics by gas chromatography and chemical

determinations such as: % dry matter, % nitrogen, % nitrogen

ash-moisture free, % ash, % calcium, % phosphorus, pH, NH ",

NO ", CL~, and bacterial plate counts (aerobes and anaerobes).

The dry matter, nitrogen determinations, and percent

ash were determined according to A.O.A.C. methods (1970), calcium

according to Hunt (1963), and phosphorus according to Sumner (1944).

Measurements for pH v;ere determined using a slurry of 5 gm

of manure and 50 ml of deionized water. The ammonia, nitrates

and chloride were determined using an Orion flodel, digital pH

meter. The specific ion electrodes used were as follows:

Orion lonanalyzer

Model 95-10 Ammonia Ion Electrode

Model 92-07 Nitrate Ion Electrode

Model 92-17 Chloride Ion Electrode

Aerobic and anaerobic microbial plate counts were determined

using standard serial dilution techniques. Nutrient agar was

used for aerobic counts and Schaedler agar for anaerobic organisms.

Duplicate plates were incubated at 37°C for 3-5 days and then counted

D

Registered trademark.

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27

ODOR PANEL

Screening Tests

Preliminary screening tests were conducted to determine

if any prospective panelists were unqualified to serve on an odor

panel. The following tests were given on two day (tests 1 and 2

on day 1):

Test 1 - Identification of Cooking Extracts

Capped brown vials were filled with ten flavor extracts

and subjects were asked to identify the odors. The following

extracts were used: maple, lemon, peppermint, orange, butter,

strawberry, vanilla, banana, coconut, and coffee.

Test 2 - Ranking of Odor Series According to Dilution

Lemon extract was diluted according to the following

percentages: 0, 0.01, 0.1, 1.0, 100. Subjects were asked to

arrange the dilutions from lowest to highest concentrations.

Test 3 - Comparison of Manure Samples Per Intensity and

Offensiveness of Odors

Duplicate manure samples of horse, sheep, dairy cow,

feedlot cattle, swine and scouring calf were mixed with water and

put into baby food jars which had been sprayed black. A thin

layer of cotton was put over each sample. Subjects were asked to

score samples according to odor intensity (not perceptible to very

intensive - part A) and odor offensiveness (not offensive to very

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28

offensive - part B). (See score sheet in Appendix)

Evaluation of Tests

Test 1 - Odor Identification

Subjects were graded according to how many odors were

identified correctly (0 - none correct to 10 - all correct).

Test 2 - Odor Dilution

The incorrect order of samples was recorded if subjects

did not arrange samples in correct order.

Test 3 - Odor Intensity and Offensiveness

Numerical values were assigned to each classification of

parts A and B. (See score sheet in Appendix). The average value

for parts A and B were compared to the group averages and scored

numerically according to the difference from the averages.

Subjects were also evaluated for consistency of duplicate

scoring (0 - no duplicates matched to 6 - all duplicates matched).

Ranking of Panelists

All tests were considered in ranking panelists. Tests 1

and 2 were evaluated together. Persons having equal results were

given equal ranking. Individual rankings were totaled and then

arranged from lowest (best) to highest (worst) scores.

The precision and accuracy of this method depends on the

number, physical condition, experience, and skill of the panelists.

The following stipulations and requirements were asked of each

Page 33: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

29

panelist:

1. Colds or other physical conditions affect the sensory

system and will interfere with panel testing. (Do not

participate if you feel your sense of smell is impaired)

2. Extraneous odors will interfere in the testing. (Do not

use such things as perfume or after-shave on the

testing day).

3. Use of tobacco and gum or even eating can affect the

sense of smell and shall not be indulged in for at

least 30 minutes prior to the evaluation of odors.

4. Wash hands thoroughly before beginning the series of

samples.

5. No comments prior to or during the odor panel.

6. Be sure to replace lids tightly on the samples after

using.

The manure samples were placed in black 1/2 pint mason

jars. Panelists were given a known standard untreated (control)

sample, and instructed to rate the other samples according to their

similarity to the standard (matching standard), 0 - 8 least similar

to most similar. Panelists were also requested to score each

sample according to intensity and offensiveness. The samples were

renumbered and then subjected to a repeat panel at a later time on

the same day. The results of both panels were than averaged.

The screening showed that some persons tested may be yery

Page 34: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

30

poor panelists. Nineteen persons participated and all of then

were non-smokers.

Camphorls was used to clear the nose between samples.

GAS CHROMATOGRAPHY

The volatile compounds were measured by gas chromatograu.iy

to separate the hydrocarbon compounds into acids and aldehydes,

and amines. This method was used to determine any relative differences

of compounds in a particular sample resulting from gypsum treatments

and no attempt was made to identify the peaks.

Gas chromatography is a technique for separating volatile

substances by percolating a gas stream over a stationary phase,

in this case solid. The components to be separated were carried

through the column by an inert gas (carrier gas). The sample

components, according to their distribution coefficients, formed

separate bands in the carrier gas. These component bands left

the column in the gas stream and were recorded as a function of

time by a detector. The written record obtained from a chromato­

graphic analysis is called a chromatogram, where the time is the

abscissa and milivolts the ordinate. Each sample analysis was

completed in approximately 20 minutes. The retention time is that

time from injection to the peak maxima. This property is charac­

teristic of the sample and the solid phase at a given temperature.

The area produced for each peak (given as a % ) , Is proportional to

that peak's concentration (McNair and Bonelli, 1969).

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31

This chromatographic trace gas analysis technique employs

a flame ionization detector. The sample size was 5 ml of gas

taken 2.5 cm above the solid waste, and drawn with a gas syringe

from the jars which were covered with Parafilm and incubated

from 1-3 hours at a temperature of about 35°C. The sample was p

then injected into the Perkin-Elmer 990 gas chromatograph at a

temperature of 225°C (to volatilize the sample), the manifold

temperature was maintained at the injection temperature, and the

general conditions of the gas chromatograph were 150°C (column

temperature), and 30-35 cc/min. flow rate for the gas carrier

(nitrogen). The columns used were 180 cm long and 8 mm of internal

diameter, 80-100 mesh chromosorb 103 for amines and 101 for acids

and aldehydes.

The study was initiated during the fall of 1973 with

data collection completed in August, 1974.

Page 36: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

RESULTS AND DISCUSSION

Values obtained (see Appendix Tables 3, 4, 5, and 6)

from the gas chromatographic analyses, showed an extreme variation

for all the peaks recorded between the control and the treatments

within one location, and also between locations. Due to ihis

variability, and several unrecorded values, it was impossible to

determine whether this variation indicated a significant reduction

in volatile compounds; therefore the results and conclusions of

this study were based upon the odor panel and chemical analyses.

It can be observed in Appendix Tables 3 and 4 however, that gypsum

treatments effected a different array of peaks on the chromatogram,

which supported the panel observations that the odor quality was

changed by treatments. The odor panel work demonstrated that the

human nose was able to detect elements in concentrations undetect­

able by the most sophisticated instrumentation of the day. There

was also evidence to indicate that these minute quantities of

odorous compounds, if isolated by themselves, might not be perceived;

but, synergistically combined with other elements present in minute

quantities, created a disagreeable odor. These observations go along

with the ones reported by Bethea (1972) and Sobel (1970b).

Results of these investigations are summarized in the

following tables. Table 1 presents the least squares means for

the paramenters measured at the Pantex and Lubbock Feedlot locations.

Mean squares from the analyses of variance for the various parameters

32

Page 37: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

33

measured are presented in Table 2. Location was an important

Influence upon most of the parameters. This effect is explained by

the feedlot surface involved rather than a strict difference due

to geographical location. At Pantex, the feedlot surface is

dirt, whereas a concrete surface was involved at the Lubbock

Feedlots. The dirt surfaced lots had waste containing significantly

lower percentages of dry matter (p<.05), nitrogen (p<c.05),

nitrogen (ash-moisture free (p<:.05), phosphorus (p<.01),

ammonia (p^.Ol), and chloride (p^.Ol), but higher values for

% ash (p<.01), % calcium (p<r.01), pH (p<c.05), aerobic and

anaerobic bacterial numbers (p^.Ol). Results of the organoleptic

test indicated nothing about the aesthetic influence of the gypsum

when used to alter the odor of animal wastes. It showed only the

degree of divergence in odor quality caused by adding the chemical

when compared to an untreated standard. The odor panel noted that

the gypsum changed the quality of the odor of the manure but the

resulting odor was not desirable and, sometimes, even more offensive

than the untreated waste.

Treatment effects in Table 1 indicate that the gypsum

and spray significantly (p<^.05) changed the smell of feedlot waste,

but the intensity and offensiveness of the treated waste was

unchanged as compared to untreated waste. The fine gypsum treatment

produced feedlot waste with a lower dry matter percentage than the

other treatments or control. The coarse gypsum significantly

(p«^.05) lowered the % dry matter as compared to the control.

Page 38: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

34

Table 1. Least Squares Means for Parameters Measured at the Pantex and Lubbock Feed Lot Locations

Parameter

Odor Panel

Matching Standard

Intensity

Offensiveness

Locat Pantex

5.2**

2.7

; 3.2

Chemical Analyses

Dry Matter,%

Nitrogen, %

Nitrogen (ash & H2O free), %

Ash, %

Calcium, %

Phosphorus,%

pH

Ammonia, %

Nitrates, %

Chloride, %

52.07*

2.4*

3.9*

39.51

4.50

0.57*'^

8.0

0.41**

0.33

2.46**

Bacterial Counts^

Aerobes

Anaerobes

4.0

2.8

ions Lubbock

5.8

2.7

3.1

55.68

3.4

4.2

20.17**

2.54**

0.68

7.6*

1.33

0.16

6.49

0.3**

0.1**

Control

6.0*

2.6

3.1

58.66**

2.9

4.2

31.08

3.44

0.64

8.0

0.79

0.26

4.29

1.6

1.3

Treatments Coarse Gypsum

5.4

2.7

3.2

53.18

2.8

4.1

32.40

4.00 •

0.60

7.7

0.91

0.25

4.43

2.1

1.4

Fine Gypsum

5.3

2.7

3.1

49.57**

2.9

4.1

28.96

3.83

0.57

7.5

0.71

0.22

4.24

3.0

1.7

Sp ray t>

5.3

2.7

3.3

54.09

2.9

3.9

26.92

2.82

0.67

8.1

1.05

0.25

4.93

-

2.0

1.4

*P<.05

**P<.01

^X 10^ per g dry matter

^Applied monthly as a mist to the waste on the feedlot surface, An exploratory product (name unknov/n) proposed tc decompose the ^^y matter. This was tesied ai Lubbock Feedlots only.

Page 39: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

35

Table 2. Mean Squares from the Analysis of Variance

Parameter

Odor

Matching Standard

Intensity

Offensiveness

Chemical

Dry Matter

Nitrogen

Nitrogen (ash free)

Ash

Calcium

Phosphorus

pH

Ammonia

Nitrates

Chloride

Bacteria^

Aerobes

Anaerobes

^Associated treatments; and '

^X 10^

& H 0

degrees 17 for w

Location

4.096

0.042

0.066

60.415

4.609

0.423

1732.234

17.781

0.060

0.820

3.914

0.138

75.209

66.470

32.113

of freedom are: ithin.

Mean Squares^

Treatments

1.580

0.027

0.047

79.035

0.020

0.047

25.337

0.961

0.007

0.337

0.091

0.001

0.322

2.039

0.152

1 for location;

Within

0.4''5

0.074

0.221

10.970

0.045

0.062

25.676

1.121

0.013

0.127

0.032

0.036

0.850

0.978

0.146

3 for

Page 40: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

36

In spite of the sophisticated technical equipment that has

been developed, the human odor sensing system remains the most

suitable detector available (Amer. Soc. Test. Mat., 1968). The

gas chromatograph can best separate and quantify odorants while

the human nose can best determine the quality and intensity of

simple or complex combinations of odorants. The capabilities of

one complements the other rather than one supplementing the other

(Stephens, 1974). The odor panel values from Table 1 showed that

the odor vyas changed among treatments and between locations.

The chemical analyses showed that the % dry matter was

significantly different (p<r-05) between locations. The % ash

was also significantly different (p-^v.lO), being higher at Pantex,

which was expected due to the dirt surface involved. The % nitrogen,

% nitrogen (ash-moisture, free), and % ammonia were also significantly

different (p<c.05, p«=::.05, and p<r.01, respectively) between

locations.

The pH was also significantly different (p*c.05) between the

two locations, being higher in Pantex (8.0) than in Lubbock

feedlots (7.6). The pH affects the solubility of many compounds.

Under conditions of high pH, hydrogen sulfide is mostly dissociated

and present as H and HS ions, resulting in few detectable odors.

If the pH is lowered, ionization decreases and the odor of hydrogen

sulfide is readily detected (Barth, 1970b). However, hydrogen sulfide

was not readily detected by the odor panel.

Page 41: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

37

Inorganic solutions rich in nitrates stimulate a growth of

algae, and abundance of algae and bacteria is favorable for the

growth of protozoa (Miner, 1969a; Loehr, 1974b). The nitrates

become a source of oxygen under anaerobic conditions. Certain

bacteria have the capability ot utilize the oxygen in nitrates and

liberate gaseous nitrogen; but since it is odorless and comprises

about 78% of the atmosphere, nitrogen can not be considered as

a pollutant (McKinney and Conway 1957). According to the values

from Table 1, nitrates were higher in Pantex than in Lubbock

Feedlots, but there was no significant difference; nevertheless

the bacterial counts for aerobes and anaerobes were higher and

significantly different (p-«c-01) in Pantex than in Lubbock Feedlots

The chemical spray changed the odor significantly (p<.05), but

it was as intensive and as offensive as the control. The other

factors measured were not altered by the spray treatment.

Page 42: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

SUMMARY AND CONCLUSIONS

Two feedlot site investigations were conducted over a

period of nine months involving two consecutive feeding periods,

with forty feedlot pens and approximately 1,200 head of cattle

per period, to determine the effect of adding gypsum to wao:^

accumulations on dirt and concrete feedlot surfaces with respect

to volatile compounds in the cattle feedlot waste. Gypsum of

two particle sizes was added to waste accumulations on the feedlot

surfaces. In addition to the field studies, a series of experiments

were conducted in the Animal Science Research Laboratory on

campus, by using fresh manure from feedlot cattle to determine

the effects of different levels of moisture and gypsum upon

volatile compounds in the manure. The various samples of cattle

feedlot waste and fresh manure, treated and untreated, were analyzed

by an olfactory panel and gas chromatography, also the chemical

determinations for % dry matter, % nitrogen, % nitrogen (ash-

moisture free), % ash, % calcium, % phosphorus, pH, ammonia, nitrates

and chloride content, and bacterial plate counts (aerobes and

anaerobes).

Gypsum, used at levels up to 30% of the dry matter in

feedlot waste or up to 75% in fresh manure and applied by hand-

spreading or in a water-slurry, changed significantly (p^.05)

the odor of the waste (Matching Standard Test), but the intensity

and offensiveness of odor was unchanged.

38

Page 43: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

39

Changes In odor were detected by peaks on the chromatograms

for amines, acids and aldehydes for fresh manure samples.

Fine gypsum significantly (p<:.01) lowered the dry matter

percentage of feedlot waste.

Gypsum did not consistently alter nitrogen and arr.rcnia

levels in cattle feedlot waste.

Fine gypsum stimulated the growth of aerobic and anaerobic

bacteria by about ten times the control numbers in the Lubbock

feedlot waste; but coarse treated samples at Lubbock feedlots

decreased bacterial numbers whereas a trend was noted for the

treated fresh manure samples to increase in bacterial counts.

Dirt surfaced feedlot pens (Pantex) had waste containing

significantly lower percentages of dry matter, nitrogen, nitrogen

(ash-moisture free), phosphorus, ammonia and chloride, but higher

values for % ash, % calcium, pH, nitrates, aerobic and anaerobic

bacterial numbers.

Page 44: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

LITERATURE CITED

Allied Chemical Company. "Industrial Use of Ozene." Morristown, New Jersey: Allied Chemical Company, Specialty Chemicals Division, Form No. 52:42.

American Society for Testing Materials. 1968 Basic principles of sensory evaluation. Amer. Soc. Test. Mater., Spec. Tech. Pub. 433.

Anon. 1972. Sagebrush for Odor Control: In the Feed or in the Manure? Feedlot Mgmt. 14:74.

Anthony, W.B. 1969. Cattle manure: Re-use through wastelage feeding. Animal Waste Mgmt. Cornell University Conference on Agri. Waste Mgmt. Syracuse, New York.

A.O.A.C. 1970 Official Methods of Analysis (11th. Ed.). Association of Official Agricultural Chemists, Washington, D.C.

Baba, Y. 1971. Deodorizing equipment and deodorants. Air Pollution Abstr. 3:53-54.

Barth, C L . 1970a. Using odor intensity limits In air quality standards. Amer. Soc. of Agr. Eng. Paper No. 72:441.

Barth, C L . 1970b. Why does it smell so bad? Amer. Soc. of Agr. Eng. Paper No. 70:416.

Barth, C.L., and L.B. Polkowski. 1971c. Identifying odorous components of stored Dairy manure. Amer. Soc. of Agr. Eng. Paper No. 71:558.

Barth, C.L.; D.T. Hill; and L.B. Polkowski. 1972d. Correlating o n and odorous components in stored Dairy manure. Amer. Soc. of Agr. Eng. Paper No. 72:950.

Bauch, H., and H. Burchard. 1972. Attempts for Improving strongly smelling or toxic effluents by Ozone. U.S. Environmental Protection Agency, Odors and Air Pollution. Washington, D.C. Govt. Printing Off. p. 87.

Benham, C L . 1967. Efl'ectiveness of Caustic Soda in preventing the development of smell in Poultry droppings slurry pits. National Agricultural Advisory Service Report. Shardlow Hall, Shardlow, Derby, England.

40

Page 45: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

41

Bentsen, P.C, and R.M. Bethea. 1969. Computerized reduction and Analysis of Gas Chromatographic Data. J. of Chromatographic Sci. 7:399.

Bethea, R.M. 1972. Solutions for Feedlot Odor Control Problems. J. of the Air Pollution Control Assn. 10:765-771.

Burnett, W.E. 1969a. Air Pollution from Animal Wastes, Dote-^in-ation of Malodors by Gas Chromatographic and Organoleptic Techniques. Environmental Science and Technology. 3:744-749.

Burnett, W.E., and N.C Dondero. 1970b. Control of Odors from Animal Wastes. Transactions of the Amer. Soc. of Aqr. Enq. 2:221.

Converse, J.C; D.L. Day; J.T. Pfeffer; and B.A. Jones, 1971. Aeration with ORP Control to suppress Odors emitted from Liquid Swine Manure systems. Livestock Waste Mgmt. and Pollution Abatement. Proc. International Symposium on Livestock Wastes. St. Joseph, Michigan. Amer. Soc. of Agr. p. 267-271 .

Cooper, G.S.; J.W. Ketcheson; and L.R. Webber, 1969. Agriculture as a contributor to Pollution. AIC Review 24(3):9-15.

Day, D.L.; E.L. Hansen; and S. Anderson, 1965. Gases and Odors in Confinement Swine Buildings. Transactions of the Amer. Soc. of Agr. Eng.

Deibel, R.H. 1967. Biological aspects of the Animal Waste Disposal Problem. Agriculture and the Quality of our Environment, ed. by Nyle C Brady. Washington, D.C Amer. Assn. for the advancement of Sci. Pub. No. 85:395-399.

Elliot, T.C 1971. Odor Control: its time is coming. Power, 6:12-13.

Faith, W.L. 1970. Food and Feed Industries. Air Pollution, vol. 3. ed. Arthur C. Stern. Academic Press, Inc. New York, p. 273.

Feedlot operators fined for odors. 1972. Texas Pollution Rep. 27:3.

FMC Corporation. Hydrogen peroxide control of sewage hydrogen sulfide. New York. FMC Corporation, Inorganic Chemicals Division, undated bull.

Grub, W.; R.C Albin; D.M. Wells; and R.Z. Wheaton, 1968. Engineering analyses of cattle feedlots to reduce water pollution. 1968 Winter meeting Aner. Soc. of Agr. Eng. Paper No. 63:929.

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Hammond, W . C ; D.L. Day; and E.L. Hansen. 1968. Can Lime and tnionne suppress odors in liquid hog manure. Agr. Eng. 49:340-343. ay

Hazen, T.E. 1972. Discussion of: Solutions for Feedlot Odor ?2"^^?^,^''°'^^^"^^- - °^ ^^e Air Pollution Control Assn. 10:771-772.

Hedrich, O.H. 1935. Odor control experiments at Pasadena. Civil Eng. 5:564-567.

Hunt, J.R., 1963. Calcium det. Can. Dept. Agri. Ottawa, Can. J. Agr. Food Chem. vol. II, July-August, p. 345.

Ilovaiskaya, N.N. et_ ai., 1972. Effect of the Gypsum content of soils on Its biological properties. Tr. Tadzh. Nauch. - Issled. Inst. Pochvoved. 15(l):130-6.

Jedele, D.B., and F.W. Andrew. 1972. Slotted-floor cold-confine­ment Beef-cattle hous-'ng. Amer. Soc. of Agr. Eng. Paper No. 72:449.

Jones, D.D.; D.L. Day, and A.C Dale, undated. Aerobic treat­ments of Livestock wastes. Univ. of Illinois at Urbana-Champaign. College of Agr. Exp. Sta. in cooperation with Purdue Univ. Agr. Exp. Sta. in Layfayette, Indiana. Bull. 737:4-5

Lasalle, R.M. Jr., and M.M. Launder 1969. Manure conservation. Animal Waste Mgmt. Cornell University Conference on Agr. Waste Mgmt. Syracuse, New York. p. 245-248.

Li H i e , R.J. 1970. Air pollutants affecting the performance of domestic animals. Government printing office. Washington, D.C. U.S.D.A. Agriculture handbook No. 380.

Loehr, R.C 1968a. Anaerobic Lagoons: Considerations in design and application. Amer. Soc. of Agr. Eng. 11:320-322,330.

Loehr, R.C. 1974b. Agr. Waste Mgmt: Problems, processes and approaches. Academic Press. New York. p. 91-94, 110-115, 120.

Ludington, D.C 1968a. Oxidation-reduction potential, control by aeration and influence on odor production and degradation of chicken manure. Unpublished Ph.D. dissertation, Purdue University. Dissertation Abstr. B 29, 4:981.

Ludington, D.C, A.T. Sobel, and A.G. Hashimoto, 1969b. Odors and gases liberated from diluted and undiluted chicken manure. Amer. Soc. of Agr. Eng.

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43

Ludington, D . C ; A.T. Sobel; and B. Gormel, 1971c. Control of odots through manure management. Amer. Soc. of Aqr. Enq. 14:771-774, 780.

McKinney, R.E., and R.A. Conway, 1957. Chemical oxygen in biological waste treatment. Sewage and Industrial Waste. 10:1097-1105.

McNair, H.M., and E.J. Bonelli, 1969. Basic Gas Chromatography 5th. Edition. Varian Aerograph.

Miner, J.R. 1970b. Raising Livestock in the Urban fringe. Agr. Eng.

Miner, J.R., and T.E. Hazen 1969a. Ammonia and Amines: components of Swine-building odor. Transactions of the Amer. Soc. of Agr. Eng

Moorman, R., Jr. 1965. Controlling odors from cattle feedlots and manure dehydration operations. J. of Air Pollution Control Assn. 15:34-35.

Nakano, N. 1968. Feeds producing odor free excreta. U.S. Patent 3, 370, 953.

Nakano, T. 1972. The example of odor control with Ozone. J. of the Pollution Control Assn. 6:359-363.

Narayan, R.S. 1971. Identification and control of Beef Cattle feedlot odors. Unpublished M.S. thesis, Texas Tech University, Lubbock.

Okuno, T. 1972. The reaction of bad odor substances with ozone. U.S. Environmental Protection Agency. Odors and Air Pollution p. 77.

Paine, M.D. undated. Chemical control of Manure odor. Great Plains Beef Cattle Feeding Handbook. Cooperative Ext. Service. Great Plains States. G.P.E.-7801.

Pomroy, R., and F.D. Boulus 1946. Progress report on sulfide control research. Sewage works J. 4:597-640.

Posselt, H.S., and A.H. Reidies. 1965. Odor abatement with Potassium Permanganate solutions. I & E.C Product Research and Development. 1:48-50.

Russell, J. 1965. Manure odors can land you in court. Farm J. 89:19,36-37.

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44

Santry, I.W. Jr. 1966. Hydrogen sulfide odor control measures. J. Water Pollution Control Federation. 3:459-466.

Satterfleld, C.N.; R.C. Reid; and D.R. Briggs 1954. Rate of oxidation of hydrogen sulfide by hydrogen peroxide. J. Amer. Chem. Soc. 76:3922, 3933.

Scarlett, H. 1972. Feedlots foul, too. Houston Post, December 4.

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Sobel, A.T. 1969a. Measurement of the odor strength of Animal manures. Cornell Univ. Conference of Agr. Waste Mgmt. p. 260-270.

Sobel. A.T. 1970b. Olfactory measurement of Animal manure odor. Amer. Soc. of Agr. Eng. Paper No. 70:417.

Stephens, E.R. 1971. Identification of odors in Feedlot operations. California Agriculture. 25:10-11.

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Viets, F.G. 1971. Cattle Feedlot Pollution. Animal Waste Mgmt. Proc. of National Symposium on Animal Waste Mgmt. p. 97-104.

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Willrich, T.L., and J.R. Miner 1971. Litigation experiences of five Livestock and Poultry producers. Livestock Waste Mgmt. and Pollution Abatement: Proc. International Symposium on Livestock Wastes. St. Joseph, Michigan. Amer. Soc. of Agr. Eng. p. 99-101.

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45

Yocum, J.E., and R.A. Duffee. 1970. Controlling Industrial Odo.-s. Chem. Eng. 77:160-168.

Yushok, W., and F.E. Bear 1948. Poultry Manure: Its preservation, deodorization and desinfection. New Jersey Agr. Exp. Sta., Rutgers University, New Brunswick, New Jersey. Bull. No. 707.

Page 50: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

APPENDIX

46

Page 51: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

o

• o

o o

3

O

(0

ro

cn O 4-> ro E o s-

sz o w ro

O

CO

0)

ro

00

c ro

• p -

u

^

ro 0)

c E 3

"o

• M C (U E +J ro 0) S-

x> c ro

+-> fO

Q

00

VO

i n

00

OJ

CO KO ^ K£> . . . .

r«» ro ro ^

\Si f^ f*^ IX) . . . .

^o ^ ' ^ f^

cr> Lo Osj r o • • • •

CD r^ r o «^ r o CM r— r o

00 r o CM «^ • • • •

CD cn Kt ^ CVJ r o CM CM

cr> o m U3 . . . .

tJD «^ r o CM

O O t o O . . . •

«:3- t o CM «:i-

O CM cx» r>. • • • •

r>v vo i n CM

ro r-* •— r— . . . .

r- 00 r- vo

f— CO 1— "Si-• • • •

«:a- vD 00 r^

LT. o^ O vo . . . .

i n r>. o lO

^ p>» r o 00 • • • •

ro CM i n sj-r o CM I— CM

00 ro ro o • • • •

i n r^ •— «vf I— CM r o CM

i n I— ^ «;}• • • • •

^o r>. *>!• i n

CM i n ^ l o . . . . «^ <d- ro ro

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ro I— r>» r— • • • •

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CM r>^ i n r^ • • • •

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CM i n l o r^ . . • .

i n «:t ^O C«J CM "td-

47 ro ro l o CM

• • • • CM r>. o^ ro I— r o CM

CM «:a- r^ r o • • • •

CM 00 CM CM

cr> i n t n o • • • *

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«d- vo o O • • • •

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I— CM i n vo * • • •

r o CM CM CM

^ m r o cy» . . . .

CM ^ CM r o

r o r o 1 ^ VD . . . .

^ i n CM <y» ro

s f I— — o 4-> C o

CO $-«o o

a; ro c s-<r- Q .

CM

i n f— — o

c o

to s-rO o

>» <D ro C $-•r— ex.

t_3 O U_ CO C_3 O Li_ GO O <-> Lx. OO O O U- t o

«o a: s-

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o o

3

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C L ro s. OS o 4-> ro E O s.

x : o

CO ro

CJ3

ro

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c E 3

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&^

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c

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c ro

(U

ro O

VO

i n

r o

00 CM r^ CM • • • •

o r^ o> CM <£> l o LO r^

o> CM r^ 00 • • • •

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!*«>. 00 CXi O • • • •

as m a t^ in ro 00 ^

i n r o o r— . . . .

l£) r o r>» «;:J-

r o r o r— vD • • • •

00 vn i n VO

i n f— VO o • • • • in o o o ro

CM CM i n CT> • • • •

m r o r o «;i-

cr> CM CO cy> • • • •

r>. <d- ^ VO

n - o^ o^ r^ . . . .

CT* 00 r o r^ CM

i n i n CO o • . . .

00 r^ VD VO

o «!t 00 r o • • • •

CM cy> r>. VO

f^ h". o ^ • • • •

VO ro CM a>

CM r o r o CTt CT»

• • t •

r— o o i n

O O CM 00 • • • •

r o CM VO I—

CM VO p^ ro • • • •

«^ r>. i n VO

I— i n CM o • • • •

00 00 cvj r^

r— crt ^ r^ • • • •

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CTk O O VO • • • •

^ VO h^ CT>

VO r>. n - 00 . . . .

o^ r o i n «vf m CM VO CM

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VD I— VD VD

r o

r o O (U $- to >>

+J S- O) lO c: ro C S-O O T - Q.

<_)<_) Uu C/)

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i n

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>> <U fO

Q. O O Lu </l

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VD ro i n 00 • • • •

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00 i n VO r— . . . .

i n ro i n CM

r>> CM CM CM . . . .

VO o^ cy> 00

ro VO 00 i n • • • •

VO 00 00 i n f— «:3- i n

CM

i n v . .^ r^

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O CJ U- 00

ro

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49

OS

00

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• — 1 — O f—

VO r^

o o

0.7

1

1 • • CM f—

1 • • o o

ovi r>H CM 00 r^ • • • . .

C M O ,— r - O

CVi , CM

X O)

c ro

CI.

o

>> JC CL ro S. Oi o +J fO E o s-

JZ

V) ro

i n

ro

to <U

TO >> x : XJ

c ro

•r— O

•a:

to

ro

VO

r^ I— cr> VO o^

ro i n VO r- 00

c E 3

'o o

i n

00 00 «5i- <T> ^

.— I— I— CM o

VO o cy> "ei- r—

I— r - O r o CM

ro

CM

00 i n CM . . I

O r - I—

VO r^ c^ VD • • • •

o o o o

4-> c 0) E

ro

X )

c ro

(U +-> ro o

r^ 00 m o i n . . . . •

i n ro CM 00 «vf ^ 00 ro ro 00

00 «;*' r o «;^ r^ • • • • •

«;t CM CO <7» ro

i n r^ rv. ro r— r - O CM I— r -

ro ro o i n CM • • . . • '— o ,— o o

CM CM r>, r - ^ • • . . .

o o o I— o

t— r«» i n o VD

f— O rsj oo o

<T> i n VO CO r>.

o o •— f— o

^O r— OS KT r— • • » . .

O O o o o

CM O LO CM VD • • . . .

o O o o o

cr> o^ ro cy» o . . . . .

CM o^ CM ^ r^ 00 00 VO i n 00

ro r~». 00 i n i n • • . • .

CM i n r o CM VO o> cr> o^ cr» o^

I I I I I

r o I—'d-

o o o

CsJ

00

r o VD «^

i n r<^ i n

' ^ «^ r^ LO i n

CM CM r— CM O

r— i n o i n i n

CM cy> C T i r o ^

ro ^ inr>.cr> O r - I — O i —

ro cn CM corn

O ro r—cy>r^ I— CM

«e- o r^ VO . • . I .

O r— I— O

I I I

CT> CM r o VO o

ro i n r^ r— <d-«vl- i n i n

ro r-. I I • • 1

r*» 00

VO <d-• •

o o

as 1 • 1

o

r^ ro

CM CM "Si- r o

I I I

CM r^ v o o o ^ CM vovoin i n <;J- vococo

^t: :»t: =*fc =tfe *r-» i n i n o o ^ . . . . r^ O O r- r -

i n

ro CM

o u 4-> c

<u to s-rO

<U c

(U to s-ro

d) C

o o O -r-O V_) Li_ O U -

CM

ro

ro

i n i n o o • • • •

O O . - r -

O s -

4-> C o

to J-<o o

to S- Q) ro C O •!-

O O Li_ O U-

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=*fe =*te :«= =»te i n i n o o

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O O r — 1 —

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Page 54: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

50

vo

f— o VO CM ro

LO I— o "d- ro

O^ VO LO VO VO . . . . .

in ro in ^ ^

r>. r^ VO «^ o

** CO CM 00 'd-

LO 00 r*. 1^ CM vp • • • • • '

VO r- CM «vr r^

VO CM r- CM ro

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ro VO LO r— VD

O CM O VD I—

X OJ 4-> c ro

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o ro E

o u sz o t/> ro C3

to

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ro

ro O <Tt d- VO O

ro o I— ro ro

CM ro CM r— ro o

ro o r^ lo CM r^ VO to LO VO

I I I ! VO 00 •— CM

o d o I— o

r* ro r— CT> o^

^ r— ro LO CM CM o^ as CM o ro

cj CM cn f— 00

ro CM f— •N ro

CM CM lO *:i-« • • • •

f— I— ro LO 00

VO

JQ ro

cn o ro CO r—

I— VD 00 CM «;t-r— ro ro ro CM

cn ro 00 ro LO • • • « •

cn LO CM ro ^ «;r r>* VO LO 00

I— r-* «^ r^ CO • • • • •

1— o ro LO cn <n cn ro 00

-p

c (U E 4-> ro <U

•o c (O

0)

ro O

=W= : tfe tte in IT) o o O C) r- r— I—

in r->v. o <u <u ro $- to «/> »— -> s. 0) s- (U CM C ro c: ro C

O O •!— O -r-Q. O O U.. CO Li-

<d-r*. '>.^ CM

*** ^ ro %_ ro O-•K

=t t :=«=^ =«= in in o o

. . . . O O r - •—

— O (U <u s- to to 4J $- <U i - <U C ro C ro C O O •«— O 'f—

CJ O U- <-> U-

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«* t-^ • ^ cn r— ^^ ro • o — ^

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Page 55: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

51

VO ^ CM LO • • •

• — O o

I I

LO i ^ 1 ^ «:f 0 0 0 0

in CM o o o

X

c ro

o

CL ro S-a^ o 4-> ro E O s-JC o {/) ro CD

to <L) C

ro «;j- in r>« • • • •

f— CM CM O ro : ^

CO

c E 3

O CJ

ro

la. ro

cn o CM in • • • • •

o o •— o o

CM in ro ro ro . . . .

o ro o o

VO

O)

!a (O h- r*. o^ VO o

• • • • • CM'd- CM VO 00 o> cn in o% CT^

c (U E

ro O S-

C ro

0) 4-> ro O

•st r>. ro CM >^ 'd-

i n

O-

=tt: =tt: =tt= =tfe

in in o o d CD 1— r—

f —

o <u <u s- to CO 4-> s- (U s- a) C ro C ro C O O 'r— O 'r-

C J O t i . o u .

ro

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Page 56: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

52

Name Time

^^^® —.^ Sample Set

Table 7. Matching Standards Method Data Sheet

Sniff the manure standard. Compare the unknowns with the standard in turn, and rate the degree of similarity on the following scale:

Extremely similar 8 7

Mery similar - 6 5

Moderately similar 4 3

Slightly similar --- 2 1

Not similar --- 0

Ignore any differences in intensity, and concentrate on

odor quality.

MANURE STANDARD ODOR

Unknowns Degree of similarity

1 -

2 - -

3 — - -

4

5 - - - -

6 - -

7 —

8 -

9 -

10 -

Page 57: CONTROL OF VOLATILE COMPOUNDS IN CATTLE FEEDLOT

53

Name_

Date

Table 8. Odor Panel Recording Sheet

Time

Sample Set

PART A

Sample #

1

2 3 4 5

6 7 8 9 10

Mery Intensive

Perceptible Slightly Perceptible

Not Perceptible

PART B

Sample

1

2

3

4 5

6 7

8

9 10

"^ery Intensive

Perceptible Slightly Perceptible

Not Perceptible