PB85-148708
Land Treatment of Petroleum
Refinery Sludges
Oklahoma Univ., Norman
Prepared for
Robert S. Kerr Environmental Research Lab.
Ada, OK
Nov 84
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
NTIS
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EPA-600/2-84-193
November 1984
LAND TREATMENT OF PETROLEUM REFINERY SLUDGES
by
Leale E. Streebin, James M. Robertson, Herbert M. Schornick,
Paul T. Bowen, Kesavalu M. Bagawandoss, Azar Habibafshar,
Thomas G. Sprehe, Alistaire B. Callender,
Charles J. Carpenter, Vickie G. McFarland
The University of Oklahoma
Norman, Oklahoma 73019
Cooperative Agreement No. CR 80757810
Project Officer
Don H. Kampbell
Source Management Branch
Robert S. Kerr Environmental Research Laboratory
Ada, Oklahoma 74820
This study was conducted
in cooperation with
The University of Oklahoma
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ADA, OKLAHOMA 74820
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TECHNICAL REPORT DATA
(Please read Inzlructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-84-193
2.
3. RECIPIENT'S ACCESSION NO.
£30 5 148708 /AS
4. TITLE AND SUBTITLE
Land Treatment of Petroleum Refinery Sludges
5. REPORT DATE
November 1984
6. PERFORMING ORGANIZATION CODE
7. AUTMORis) L.E. Streebin, J.M. Robertson, H.M. Schornick,
P.T. Bowen, K.M. Bagawandoss, A. Habibafshar, T.G. Sprehc
B. Callender, C.J. Carpenter, V.G. McFarland
8. PERFORMING ORGANIZATION REPORT NO.
3. PERFORMING ORGANIZATION NAME AND ADDRESS
School of Civil Eng. & Env. Science
University of Oklahoma
Norman, OK 73019
10. PROGRAM ELEMENT NO.
CBRD1A
11. CONTRACT/GRANT NO.
CR807578
12. SPONSORING AGENCY NAME AND ADDRESS
R.S. Kerr Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
P. 0. Box 1198, Ada, OK 74820
13. TYPE OF REPORT AND PERIOD COVERED
Final 04/80 - 06/83
14. SPONSORING AGENCY CODE
EPA/600/15
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Petroleum API Separator sludge was applied to field plots to evaluate optimizatio
of loading rates and frequencies for waste disposal by land treatment. Loading rates
3 to 13 weight percent end frequencies 1 to 12, respectively, per year were studied
over an 18 month period. Total oil losses were proportional to the amount applied
and averaged 54 percent over the study period. Saturates fraction loss was highest
followed by aromatics, polars, and asphaltenes. Volatile losses were substantial at
application, but relatively small over the long-term. Biodegradation of the oil
followed first order kinetics with a rate coefficient of 0.003 day" . Heavy metals
were immobile in the top 30 cm zone of incorporation. Facility design factors are
discussed relating to field equipment operation, oil percolation prevention, runoff
control, and proper tillings.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Waste treatment
Organic wastes
Petroleum refining
Solid waste
Land treatment
Heavy metals
Petroleum sludge
13B
13. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport/
21. NO. OF PAGES
334
Release to public
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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NOTICE
Although the research described in this document has
been funded wholly or in part by the United States
Environmental Protection Agency through assistance agree-
ment #CR80757810 to The University of Oklahoma, it has
not been subjected to Agency review and therefore does
not necessarily reflect the views of the Agency and no
official endoresement should be inferred.
ii
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FOREWORD
EPA is charged by Congress to protect the Nation's land, air, and water
systems. Under a mandate of national environmental laws focused on air and
water quality, solid waste management and the control of toxic substances,
pesticides, noise, and radiation, the Agency strives to formulate and imple-
ment actions which lead to a compatible balance between human activities and
the ability of natural systems to support and nurture life.
The Robert S. Kerr Environmental Research Laboratory is the Agency's
center of expertise for investigation of the soil and subsurface environment.
Personnel at the Laboratory are responsible for management of research pro-
grams to: (a) determine the fate, transport and transformation rates of
pollutants in the soil, the unsaturated zone and the saturated zones of the
subsurface environment; (b) define the processes to be used in characterizing
the soil and subsurface environment as a receptor of pollutants; (c) develop
techniques for predicting the effect of pollutants on ground water, soil and
indigenous organisms; and (d) define and demonstrate the applicability and
limitations of using natural processes, indigenous to the soil and subsurface
environment, for the protection of this resource.
The report contains technical information useful to those responsible
for making decisions on operational aspects for oily residue waste disposal
at land treatment facilities. Topics covered are (1) design criteria for
loading rates, frequencies of applications, and tilling frequency, (2) fate
of the waste's priority pollutants, and (3) atmospheric emissions assessment.
Clinton W. Hall
Director
Robert S. Kerr Environmental
Research Laboratory
iii
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ABSTRACT
The purpose of this study was to identify, evaluate
and optimize the factors which influence land treatment
of oily residues. A research site owned by the Universi-
ty of Oklahoma was used. A total of 50, 6.1 mx 2.7 m (6
ft x 9 ft), plots were prepared and API Separator sludge
was applied to the plots at loading rates between 3 and
13 weight percent per year, and loading frequencies from
1 to 12 times per year. The soil was analyzed for oil
content, selected heavy metals, selected organic priority
pollutants, pH, nitrate and chloride, over a 18 month pe-
riod. Oxygen levels in the soil atmosphere, and the
emission rate of volatile hydrocarbons were monitored. A
laboratory study to identify and quantify volatile hydro-
carbons emitted was also performed. Fractionation analy-
sis of sludges and recovered oils were done for sat-
urates, aromatics and polar compounds and asphaltenes.
Total oil losses were proportional to the amount of
oil applied with mean losses over the study period equal
to 54 percent of the oil applied. Losses of the satu-
rates fraction were highest followed by aromatics, polar
compounds, and asphaltenes. Volatile losses as a per-
centage of the oil applied were relatively small over the
long term, but were substantial in terms of short term
losses immediately after application. Biodegradation of
both total oil and individual oil fractions followed
first-order reaction kinetics. A composite first-order
iv
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biodegradation rate coefficient of 0.003 day~ was com-
puted after compensation for volatilization.
.Site monitoring determined that heavy metals were
immobilized and the organic priority pollutants were de-
graded in the zone of incorporation (top 30 cm) . Some
build-up of metals occurred over the study period.
Operational considerations such as sludge loading
rates and frequencies, proper tillage of the zone of in-
corporation, prevention of oil percolation and runoff,
and operation of field equipment after sludge application
are important factors in the design of land treatment fa-
cilities.
This report was submitted in fulfillment of Coopera-
tive Agreement No. CR80757810 by the School of Civil En-
gineering and Environmental Science, University of
Oklahoma under the sponsorship of the U.S. Environmental
Protection Agency. The report covers a project period
from April, 1980 to April, 1983 field and lab work was
completed in June 1983.
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CONTENTS
Abstract ill
Figures v
Tables viii
Acknowledgement xii
Notice xiii
1. Introduction 1
2. Conclusions and Recommendations 6
Conclusions 6
Recommendations 7
3. Literature Review 8
4. Design and Operation of the Land
Treatment Site 29
Site Selection 29
Site Description and Characteristics.. 31
Site Design and Construction 34
5. Procedures 46
Sampling Methods 46
Analytical Analysis 52
Analytical Methods 63
6. Results and Discussion 82
Fractionation Studies 113
Unsaturated Zone Monitoring 123
Laboratory and Field Studies 126
The Effect of Tilling on the Rate
of Emissions 153
Statistical Analysis of Data and
Development of Model 154
Analysis of Gas Chromatographic Data.. 161
Fate of Priority Pollutants 166
Unsaturated Zone Monitoring 172
Fate of Metals in Soil 174
Modeling and Design of Land Treatment
Systems 178
Bibliography 191
Appendices
A. Oil loading and content data 197
B. Volatile emissions data 273
C. Heavy metal data 311
Preceding page blank
vii
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FIGURES
Figure Page
4.1 Land treatment research site location 30
4.2 Typical vertical soil profile at site 35
4.3 Partial view of land treatment
facility 37
4.4 Sludge applicator 38
5.1 Method of installation of soil pore
water sampler 50
5.2 Vacuum soil moisture sampler 51
5.3 Land treatment simulation apparatus
used in the field 53
5.4 Land treatment simulation apparatus
used in the lab 54
5.5 Air monitoring equipment set up in the
field 55
5 .6 Sample concentrator 58
5.7 Stripping test setup 75
6.1 Total loss (%dwb) vs time loading moment,
first year data 93
6.2 Percent (dwb) lost per day vs total
percent (dwb) applied to date 97
6.3 Calculated total volatile emission of
sludge sample vs time 129
6.4 Relationship between cumulative total
volatile mass and sludge weight loss 130
viii
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FIGURES (continued)
Figures Page
6.5 The effect of loading rate and tilling
frequency on emission in laboratory
experiments at 60°F 131
6.6 The effect of loading rate and tilling
on total hydrocarbon loss in field
studies 132
6.7 Rate of emission of volatiles in first
two hours after application at tempera-
tures 30°F and 60°F 134
6.8 Rate of emission of volatiles in first
two hours after application at tempera-
ture 80°F 135
6.9 Percent volatile loss at different
loading rates vs time 140
6.10 The effect of loading rate and tilling
frequency on emission in laboratory
experiments at 35°F 145
6.11 The effect of loading rate and tilling
frequency on emission in laboratory
experiments at 85°F 146
6.12 The effect of temperature on emission
at 3% loading rate 148
6.13 The effect of temperature on emission
at 6% loading rate 149
6.14 The effect of temperature on emission
at 10% loading rate.. 150
6.15 Total 7-day loss as a function of
variable temperatures and loading rates... 151
6.16 The effect of increased relative humidity
and moisture content on emission 152
6.17 Time relation of emission rate and
loading rate - Benzene 164
ix
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FIGURES (continued)
Figures Page
6.18: Time relation of emission rate and
- temperature - Benzene 165
6.19 Chromatogram of air sample taken from
plot 4 (before tilling) 167
6.20 Chromatogram of air sample taken from
plot 4 (after tilling) 168
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TABLES
Page
CHARACTERISTICS OF REFINERY SOLIDS WASTES.. 10
GRADATION ANALYSIS OF SURFACE SITE SOILS... 32
DRY DENSITY - OPTIMUM MOISTURE ANALYSIS
RESULTS 33
4.3 PLASTICITY ANALYSES 34
4.4 TOTAL CUMULATIVE OIL LOADINGS -
1981, 1982 43
5.1 STATISTICAL ANALYSIS FOR CHOICE OF
SAMPLER 48
5.2 EXPERIMENTAL CONDITIONS FOR LABORATORY
STUDY 62
5.3 COMPARISON OF OIL CONTENT ANALYSIS
METHODS 66
5.4 GC CONDITIONS FOR PRIORITY POLLUTANT
ANALYSIS 69
5.5 POLLUTANTS IDENTIFIED AND QUANTIFIED IN
AIR SAMPLES ALONG WITH THEIR RETENTION 72
5.6 PURGE & TRAP AND CHROMATOGRAPHIC
CONDITIONS FOR THE ANALYSIS OF HYDROCARBON
COMPONENTS 74
5 . 7 OIL RECOVERY FROM SPIKED SAMPLES 78
5.8 RESULTS OF ANALYSIS OF KUWAIT CRUDE OIL
FOR QUALITY CONTROL - ANALYST 1 79
5.9 RESULTS OF ANALYSIS OF KUWAIT CRUDE OIL
FOR QUALITY CONTROL - ANALYST 2 79
xi
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TABLES (continued)
Table Page
6.1 PLOT ALLOCATION TO VARIOUS DATA
- ' EVALUATIONS 90
6.2 TOTAL LOSSES DURING FIRST STUDY YEAR 92
6.3 TOTAL LOSSES DURING SECOND STUDY YEAR .. 94
6.4 TOTAL LOSSES DURING TWO YEAR STUDY PERIOD.. 96
6.5 KINETIC ORDER AND LOSS RATES FOR FIRST
STUDY YEAR 99
6.6 KINETIC ORDER AND LOSS RATES FOR THE
SECOND STUDY YEAR 102
6.7 RATE COEFFICIENTS FOR 1983 (BASED ON 30 DAY
INTERVAL IMMEDIATELY AFTER APPLICATION 104
6.8 LOSS RATE COEFFICIENTS FOR CYCLIC OIL
LOSS DATA (1982) 105
6.9 TOTAL VOLATILE LOSS FROM FIELD PLOTS 109
6.10 PORTION OF TOTAL LOSS AS VOLATILE
EMISSIONS Ill
6.11 FIRST ORDER LOSS RATES CORRECTED FOR
VOLATILE LOSSES 112
6.12 AMOUNT OF OIL AND OIL FRACTIONS APPLIED
TO PLOTS 30 and 35 114
6.13 MEAN CONCENTRATIONS OF OIL FRACTIONS -
PLOT 30, 35 116
6.14 TOTAL LOSSES * OF OIL FRACTIONS 117
6.15 TOTAL OIL AND OIL FRACTION LOSSES 121
6.16 FIRST-ORDER RATE COEFFICIENTS FOR OIL
FRACTIONS 121
6.17 OIL LOSSES - COMPARISON WITH REPORTED
VALUES 124
6.18 OVERALL LOSSES OF OIL FRACTIONS 124
xii
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TABLES (continued
Table Page
6.19;.. OIL CONTENT ANALYSIS OF THE UNSATURATED
ZONE 125
6.20 STRIPPING TEST RESULTS 127
6.21 TOTAL VOLATILE LOSS FROM FIELD PLOTS 136
6.22 PERCENT OF TOTAL LOSS FROM DIFFERENT
LOADING RATES AT DIFFERENT TIMES FROM
APPLICATION 139
6.23 MEAN AND STANDARD DEVIATION OF TOTAL
AMOUNT OF SLUDGE APPLIED AND TOTAL
VOLATILE LOSS 142
6.24 TOTAL VOLATILE LOSS FROM LABORATORY
EXPERIMENT 144
6.25 RATE OF EMISSION AND EQUILIBRIUM
CONCENTRATION OF HYDROCARBONS AFTER
SLUDGE APPLICATION 160
6.26 BOILING POINTS AND VAPOR PRESSURES
OF MEASURED COMPOUNDS 162
6.27 PRIORITY POLLUTANTS PRESENT IN THE OILY
RESIDUES, BATCH I 169
6.28 PRIORITY POLLUTANTS PRESENT IN THE OILY
RESIDUES, BATCH II 169
6.29 PRIORITY POLLUTANTS PRESENT AT DIFFERENT
TIMES FOR PLOT NO. 30 170
6.30 PRIORITY POLLUTANTS PRESENT AT DIFFERENT
TIMES FOR PLOT NO. 35 171
6.31 ORGANIC PRIORITY POLLUTANTS FOUND IN THE
UNSATURATED ZONE 173
6.32 BACKGROUND METAL CONCENTRATIONS IN SITE
SOIL 175
6.33 METALS APPLIED OIL (mg/kg) 175
6.34 CONC. OF METALS IN PLOT 8 176
xiii
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TABLES (continued)
6.35 CONG. OF METALS IN PLOT 13 176
6.36:.. CONC. OF METALS IN PLOT 20 177
6.37 CONC. OF METALS IN PLOT 26 177
6.38 COMPARISONS OF METAL CONC. PRESENT IN
SOIL WITH AMOUNTS APPLIED 179
6.39 METAL CONCENTRATION IN DEEP CORES (mg/kg).. 181
6.40 ACCEPTED METAL CONCENTRATIONS IN SOIL
AS A RESULT OF IRRIGATION OF OTHER
ACTIVITIES 182
6.41 EQUILIBRIUM VALUES ASSUMING
K = .003 DAY"1 187
6.42 EQUILIBRIUM VALUES ASSUMING OTHER
RATE COEFFICIENT 188
xiv
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ACKNOWLEDGEMENTS
The authors acknowledge Drs. Edwin Klehr and Joakim
Laguros of the School of Civil Engineering and Environ-
mental Science at the University of Oklahoma for their
assistance and advice on this project and Drs. Eric
Enwall and Tom Carne of the Chemistry Department at the
University of Oklahoma who assisted with the GC/MS work.
We acknowledge Dr. Don Kampbell and Mr. Leon Myers of the
Robert S. Kerr Environmental Research Laboratory for
their assistance and guidance during this project. Cindy
James, Nancy Laudick and Upendra N. Tyagi assisted with
the analytical work. Finally, we would like to express
our sincere appreciation to Barbara Jones and Betty Craig
for their efforts in preparation of the manuscript.
XV
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SECTION 1
INTRODUCTION
Land treatment of various wastes has been practiced
world-wide for more than 100 years. Municipal wastes and
sludges were probably the first such wastes to be spread
on the land. This practice was no doubt influenced by
the fertilizer value of these wastes. Many industrial
wastes have also been applied to land for treatment and
disposal. In the past 25 years, land treatment of
sludges from petroleum refineries has become a more
frequently used process. Recently, it was reported that
9 percent of the refinery sludges were disposed of by
land treatment in 1973 with an increase to. 34 percent
projected by 1983 (Adams and Koon, 1977) .
Work completed to date shows that land treatment can
be an effective and environmentally safe procedure for
oil and biological sludges. Migration of heavy metals
can be controlled by maintaining aerobic conditions and a
pH above 6.5 (Fuller 1977, Dibble and Earth 1979,
Francsen 1980, and Huddleston 1979). One potential prob-
lem resulting from land treatment of refinery sludges is
leaching of organics through the unsaturated zone to the
ground water. Leaching is addressed in this study. When
land area is readily available, land treatment is usually
more cost effective than the other disposal techniques,
including landfilling. The relative simplicity of the
process is a major advantage. However, process simplic-
ity can also lead to quick abuse. For example, the oper-
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ator may not distribute sludge evenly over the land
treatment site, but may discharge the contents of the
tanks over the dike onto the site without distribution or
entrainment.
»
When oil is applied to soil, losses occur through
volatilization, downward migration, biodegradation and
photodegradation. A high percentage of the volatiliza-
tion takes place during and immediately after application
and tilling. After a few days volatilization approaches
a baseline level and decreases at a very slow rate for
several months. Losses through volatilization and mi-
gration are undesirable, while losses through photode-
gradation and biodegradation are desirable. It is pre-
ferable to maximize the biodegradation process and min-
imize the rate of volatilization and migration to avoid
environmental adversities. It is also important to know
if any pollutants are released into the environment, be-
yond the limited'soil treatment zone.
A review of the literature published relating to
land treatment of petroleum industry residues was carried
out. Site visits and personal interviews were also con-
ducted for several refineries in Oklahoma. Limited in-
formation exists concerning site selection, site prepara-
tion, run-off control, and sludge application techniques.
The response of crops in sludge treated areas and the re-
lation of vegetation to the process, has also been re-
ported.
Many questions about the process are unanswered.
The most important questions relate to potential migra-
tion of constituents, basic design criteria for loading
rates and application practices. Optimization of the
process has not been completely defined. Site life,
closure and unsaturated zone monitoring are also topics
on which very little information exists. An increase in
. 2
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usage of land treatment processes and the strict regula-
tions outlined in the U.S. Resource Conservation and Re-
covery Act, suggest the establishment of valid design
guidelines for certain industries is urgently needed.
Because petroleum refineries constitute one of the top
ten industrial waste generators and was in 1981 among the
fastest growing in the nation this study was undertaken.
The major objectives of the study are as follows:
(1) Determine the design criteria for the land
treatment process as it applies to oily resi-
dues. The criteria are loading rates and ap-
plication frequencies and tilling frequency.
(2) Study the fate of selected priority pollutants
commonly present in oily residues.
(3) Assess the atmospheric emissions from land
treatment application of oily residues.
To accomplish this study a land treatment research
site was established near the University of Oklahoma cam-
pus. A total of 32 test plots and 8 control plots, each
6.0 m x 2.7 m (20 ft x 9 ft), were established. A 4 x 4
factorial experiment was proposed with loading rate and
loading frequency as the two variables. Duplicate com-
binations of loading rates and frequencies were estab-
lished.
The experimental design, including loading rates and
frequencies, were modified as the study progressed. The
final design is discussed in the appropriate sections of
this report. The loading rates and frequencies were
modified because of unfavorable antecedent soil condi-
tions and climatic conditions. Higher than average rain-
fall made oil application and tilling impossible for
months at a time. At the higher loading rates, it was
not possible to apply all the sludge at one time because
the soil became oil/water saturated and excess sludge
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would run off the plot. Therefore, applications at high
loading rates were split and applied over two or more
days- On some occasions, rain forced the second applica-
tipn'-.to be postponed or eliminated, thus the loading
rate/frequency for that plot was altered.
The soil of the zone of incorporation, top 30.0 cm
(11.8 in) of the research plots was sampled for oil con-
tent, pH, moisture content, and nutrients usually just
prior to application of oily residues. This sampling pro-
gram was established so rates of degradation could be
determined.
The fate of selected organic and inorganic priority
pollutants was determined on two plots with loading rates
of 10 percent and 6 percent, and at application frequency
of 2 times per year. The plots were sampled 8 times in
15 months. The samples were analyzed for the priority
pollutants suspected in the oily residues, as well as
possible degradation products. Samples were collected
from the top 30.0 cm (11.8 in) for such analyses.
Samples were also taken below the zone of incorporation
to detect which priority pollutants were migrating
vertically.
In assessing atmospheric emissions from land treat-
ment, the objectives were 1) to determine the rate and
magnitude of fugitive hydrocarbon emissions from land
treatment of refinery sludges, 2) to identify the rela-
tive effects of such parameters as sludge loading rate,
temperature, soil moisture content and relative humidity
on the magnitude of hydrocarbon emissions, 3) to identify
and quantify individual compounds being emitted to the
atmosphere, and 4) to develop a statistical model to pre-
dict the total volatile emissions rate based on the above
mentioned variables.
Limited oil content monitoring from the unsaturated
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zone of heavily loaded plots was performed to determine
the extent of migration of oil below the zone of incorpo-
ration.
vF.ractionation studies were conducted on two moder-
ately loaded plots to investigate the loss kinetics of
individual oil fractions. A fractionation scheme sep-
arated the recovered hydrocarbons into four fractions:
saturates, asphaltenes, aromatics, and polar compounds.
From a process standpoint none of the individual
plots reached equilibrium in two years. An estimate of
four to five years is required to reach equilibrium.
Therefore, an additional two to three years would be
needed to more fully evaluate the land treatment process
for equilibrium biokinetics. The biodegradation process
for the study followed psuedo-first-order reaction kin-
etics for both total oil and individual oil fractions. A
simplified single-substrate model was developed for pos-
sible use in process design and operation.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
CONCLUSIONS
The project demonstrated that land treatment is a
viable method for treatment of API separator sludge.
Annual loading rates should be based on projected
equilibrium oil concentrations not exceeding 12
percent oil with an individual application maximum
of 4 percent oil.
Soil should be tilled just preceeding application
and then immediately following to increase the soil
sorption and holding capacity, respectively.
Proper surface slopes are important to maintain
adequate drainage and control erosion.
Rototilling under proper moisture conditions is
important. Tilling under "wet" conditions resulted
in undesirable physical changes while tilling under
very dry conditions was not beneficial.
Losses of oil by degradation followed pseudo first-
order kinetics.
Variation between sample replicates and detection-
limiting concentrations hindered monitoring the fate
of priority pollutant present in the applied waste.
Volatile emissions accounted for about 2/3 of the
losses at application, but only approximately 6
percent of the total losses over a several month
period. Hydrocarbon emissions did not exceed 1979
National Air Quality Standards.
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RECOMMENDATIONS
1. ^Further studies to reinforce the projects findings
;.'.Should include optimization of tillage methods under
variable soil moisture conditions and soil types.
2. The influence of climate variability of waste con-
stituents in petroleum refinery sludges, potential
for air pollution, long-term effects of waste
application, closed site revegetation, and moni-
toring requirements are areas needing further
research.
3. Full scale studies to determine waste generation,
waste characteristics, storage, and land require-
ments are recommended.
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SECTION 3
LITERATURE REVIEW
The petroleum refining industry generates large
amounts of waste each year, a sizeable proportion of
which is classified as hazardous. Galloway (1979) re-
ported on an EPA survey which placed the amount of hydro-
carbons in refinery solid wastes at 169,465 metric tons
per year.
The individual process streams which contribute to
this quantity are listed below (Rosenberg et al., 1976).
1. Crude tank bottoms - solid sediment from incom-
ing crude oil, which has accumulated at the
bottom of the crude oil storage tanks.
2. Leaded or non-leaded tank bottoms - solids
which settle to the bottom of product tanks.
3. API separator sludge - solids which settle in
the API separator during primary wastewater
treatment.
4. Neutralized HF alkylation sludge - alkylation
sludge produced by both the sulfuric acid and
hydrofluoric acid alkylation processes.
5. Kerosene filter clays and lube oil filter clays
- clays used to remove color bodies, chemical
treatment residues, and traces of moisture from
product streams.
6. Once-through cooling water sludge - sludge from
primary settling tanks used for cooling water.
7. Dissolved Air Flotation (DAF) float - generated
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when dissolved air flotation is used to remove
oil and solids from wastewater streams.
T'8. Slop oil emulsion solids - solid fraction of
;; oil skimmed from API separators.
7 *»
9. Spent lime from boiler feedwater treatment.
10. Cooling tower sludge - sludge which settles out
in the cooling tower basin.
11. Exchanger bundle cleaning sludge.
12. Waste biosludge - excess sludge from biological
treatment of refinery aqueous waste streams.
13. Storm water silt - silt which collects in the
stormwater settling basins.
14. Fluid Catalytic Cracker (FCC) catalyst fines -
generated when catalyst is regenerated by burn-
ing off coke produced during usage of the cata-
lyst. Collected by electrostatic precipitators
or similar pollution control devices.
15. Coke fines.
16. Spent catalysts.
17. Chemical precipitation sludge - produced when
chemical coagulation is used .to remove suspend-
ed matter from aqueous waste streams.
18. Vacuum filter or centrifuge cake.
19. Silica gel - used to remove water from instru-
ment air.
DAF float, slop oil emulsion solids, heat exchanger
bundle cleaning sludge, API separator sludge and leaded
tank bottoms are classified as hazardous by the Environ-
mental Protection Agency (CFR Title 40, July 1982).
Table 3.1 lists the characteristics of some refinery
solid wastes. The wastes with highest oil content are
API separator sludge, DAF float, tank bottoms and vacuum
filter sludges.
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TABLE 3.1. CHARACTERISTICS OF REFINERY SOLIDS WASTES
Typical Composition, Percent
Oil or
Waste Type Hydrocarbon
API Separator Sludge
Tank Bottoms
Chemical Treatment
Sludge
Air Flotation Froth
Precoat Vacuum Filter
Sludges
15
48
5
22
22
Biological Treatment Sludges
Raw 0
Mechanically Thickened 0
Centrifuged 0
Vacuum Filtered
Screw Pressed
Water Treatment Sludge
Cross, F.L. and J.R. Lawson
0
0
0
, "A New
Volatile
Water Solids
66 6
40 4
90
75
29
98 1.5
94 4
85 10
75 15
40 40
95
Petroleum Refinery" . American
Inert
Solids
13
8
5
3
49
0.5
2
5
10
5
Institute
Characteristics
Fluid slurry of oil,
water and sand
Oil-water mixture
Slightly viscous
fluid
Thick, oily fluid
Temperatures
Water Consistency
Thick, but pumpable
Viscous-peanut
butter consistency
Wet crumbly solid
Intact, solid cake
Pumpable fluid, some-
times gelatinous
of Chemical
Engineering Symposium Series, Vol. 70, No. 136, P. 812.
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Land Treatment Management Practices
Several researchers have investigated land treatment
of oily residues in the last few years. These include
Kincannon, 1972; Raymond, Hudson and Jamison, 1976;
Cresswell, 1977; Odu, 1978; Dibble and Bartha, 1979;
Meyers and Huddleston, 1979; Huddleston, 1979; and Lewis
(undated).
Kincannon (1972) evaluated land treatment of three
different oily wastes during an 18 month project. Three
sludges, crude oil tank bottoms, a high molecular weight
fuel oil and a waxy raffinate were investigated. Three
test plots for each sludge were evaluated.
For a given sludge each test plot was treated iden-
tically except for soil nutrient additions. Fertilizer
additions ranged from zero to heavy. The plots were
located within the Shell Oil Company refinery at Deer
Park, Texas. The plots were located in an area where oil
wastes have been previously disposed on the land, thus
residual oil was initially present in the soil. Ferti-
lizer additions were based on agricultural experience.
Initially, nitrogen was added to the test plots in
quantities if 1,000;500; and 0 pounds per acre (urea).
Similarly phosphorous (calcium hydrogen phosphate) was
added at rates of 200;100; and 0 pounds per acre (P_05).
Further nutrients were added to the plots during the
study. No attempt was made to grow crops on the plots.
Residual oil in the soil was approximately ten per-
cent as a result of previous use of the soil area for
oily waste disposal. The oil content of the soil
returned to approximately residual levels within six to
seven months of application, but was not observed to
decrease below this point. Oil disappearance rates were
greater for those plots where fertilizer was added than
where no fertilizer was used. Oil removal rates markedly
11
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slowed in winter. Analyses of metal content in the soils
was inconsistent and no conclusions were possible.
Analyses of soil cores indicated oil and nutrients did
not infiltrate to the 2, 4 and 6 foot depths. Oil was
present at the 2 foot depth at the start of the study.
The author concluded both aromatic and saturated
hydrocarbons were reduced with time in the soil for crude
oil tank bottoms and bunker fuel oil. Organic acids were
absent from the oil added to the soils but present in
each sample of the extracted oil. The total saturates
simultaneously decreased.
Other general project observations include:
1. Major species of microorganisms present are
members of the genus Pseudomonas, Flavobacter-
ium, Nocardia, Corynebacterium and Arthro-
bacter.
2. Rainfall runoff water contained 30 to 100 ppm
oil.
3. Cost of soil cultivation was estimated to be
$3.00 per barrel of sludge at 33 percent oil.
Raymond, Hudson and Jamison (1976) reported on a
study in which six oils were subjected to land treatment.
The oils used were: crankcase oils from cars, used
crankcase oil from trucks, Arabian heavy crude oil,
Coastal Mix crude oil, home heating oil No. 2 and resid-
ual fuel oil No. 6. The oils were tilled into 10 to 15
cms of soil, with monthly tilling for the first three
months followed by quarterly tilling afterwards. Reduc-
tion in oil concentration , 48.5 to 20 percent, and rates
3 32
of degradation up to 2.4 m /4xlO m per month were ob-
served. No oil loss via water movement was observed in
run-off, leachate or soil. Vegetative growth was still
inhibited nine months after application. Significant
increases in hydrocarbon utilizing microorganisms were
12
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observed in all treated plots.
The authors noted problems in obtaining good mixing
of oil and soil, resulting in variability in the analyt-
ical-results. No great differences in degradation of
alkanes and aromatic compounds were observed.
There are essentially three ways of disposing of
these refinery solid wastes. These are landfilling, in-
cineration and land treatment. Of these three, land
treatment is rapidly becoming the most popular, because
it is relatively inexpensive (Grove 1978), and is thought
to be environmentally safe. Incineration is expensive,
while landfilling does not treat the waste, but merely
stores it in the ground, where it becomes a potential
source of ground water contamination.
Disposal of oily residues by land treatment has been
practiced for the last 20 to 25 years, but has only be-
come widely used since around 1970. In this method, the
wastes are applied to the soil, tilled or disced into the
top 15 to 20 cms (10 to 6 in) , nutrients added, and
allowed to biodegrade.
C.resswell (1977) identified the primary factors af-
fecting the degradation of oily residues as:
(1) petroleum composition
(2) temperature
(3) nutrients
(4) oxygen availability
(5) water content of soil
(6) soil pH.
Cresswell found that biodegradation was a relatively slow
process, and a loading rate of 5 percent in the top 6
inches of soil will result in the degradation of about 60
barrels of oil/acre/year. Paraffinic oils are more
rapidly degraded than asphaltic oils. He found for oil
concentrations under 10 percent, the mass of oil degraded
13
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per unit mass of soil increases with increasing oil con-
centration. Management practices consisted of rototill-
ing ,the top 6 inches of soil monthly, and maintaining
ammoAium nitrogen and orthophosphate levels above 50
mg/kg and 30 mg/kg, respectively.
Meyers and Huddleston (1979) reported on field work
on land treatment of oily residues. They added fertiliz-
er to achieve C:N ratios of 1:400 and 1:800, and a C:P
ratio of 1:5000. No difference in the rate of degrada-
tion was noted between plots with the two C:N ratios dur-
ing the first year of the study. The amount of nitrogen
added was doubled in the second and third years of the
study, to ensure that enough was being added to the soil.
The authors found all oil fractions were degraded at low
(5 percent) loading rates. Plant cover could be main-
tained to maximize oil degradation at this loading rate.
Tilling became more important at higher loading rates.
Huddleston (1979) in a general review of land treat-
ment describes the advantages of land treatment as:
(1) effectiveness of a comparatively reasonable
cost,
(2) relative environmental safety,
(3) use of natural processes that recycle the
waste,
(4) process simplicity,
(5) possible improvement of soil structure and fer-
tility.
He identified the major operational parameters as:
(1) controlling pH between 7 and 9,
(2) oil content loading of between 5 and 10
percent,
(3) moisture content of soil between 6 and 22 wt
percent depending on soil type i.e. between 50
and 80 percent of soil water-holding capacity,
14
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(4) blending of waste and soil by tilling or disc-
ing every 4 to 8 weeks.
,Dibble and Bartha (1979) monitored oily sludge deg-
rad.atipn by CO- evaluation and analysis of residual
hydrocarbons. They identified the following parameters
as important in optimizing the process:
(1) soil water holding capacity of 30 to 90
percent,
(2) pH of 7.5 to 7.8,
(3) C:N and C:P ratios of 60:1 and 800:1, respec-
tively,
(4) temperature of 20°C or above,
(5) application rate of 5 percent wt/wt oil in
soil,
(6) frequent small applications rather than a sin-
gle large application.
They also found that the addition of micronutrients and
organic supplements was not beneficial to the degradation
process.
Lewis reported on sludge farming at Exxon's Bayway
Refinery and Chemical plant. Plot studies at this plant
indicated that loadings of 150 tons/acre/year of oils and
solids were possible without overloading the soil or
producing any oil run-off contamination. The management
techniques used consisted of:
(1) Maintaining a soil pH of 7.0 to 7.5.
(2) Maintenance of nitrates and phosphates at 20-30
mg/kg by applying commercial fertilizer 2 to 3
times per year.
(3) sludge applications to the top 6 inches of soil
to achieve an oil content of 8-9 percent. The
oil content was allowed to decrease to 2-4 per-
cent before the next application of sludge.
(4) Weekly discing of the till zone to promote oil
15
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degradation.
The author notes that the management practices
described above resulted in a loading rate of 450 tons
per '.acre of oil solids and water, or 100 tons per acre of
oil alone.
Microbial Degradation of Oil Fractions
Johnson, Cook and Westlake (1972) in a study of
crude oil utilization by bacteria, found that the satu-
rate fraction was used preferentially by the microorga-
nisms. In another study in 1979, Jobson et al., showed
that the use of fertilizers increased the rate of uti-
lization of the saturate fraction as well as the bacteri-
al count.
Cansfield and Racz (1978) reported degradation of
all components of hydrocarbon residues from crude oil
storage tanks. Of the total residues applied, 50.4
percent were degraded in 833 days. Saturates were
degraded 54.6 percent, monoaromatics 50.5 percent, diaro-
matics 57.1 percent, and polyaromatic and polar compounds
44.4 percent. High molecular weight material such as
asphaltenes only degraded 11.1 percent. They reported
that the alkanes degraded to low levels in the first 106
days. The polar fraction increased and then decreased.
This speculated that degradation of all fractions would
occur through the formation of polar compounds.
Davis (1967) also reported work showing paraffinic
hydrocarbons (alkanes) in the medium molecular weight
range were oxidized more readily than either low mole-
cular weight paraffins, or heavy paraffinic fractions.
Aromatic fractions were more difficult to degrade than
paraffins.
Westlake et al., (1978) investigated in-situ degra-
dation of oil in a soil of the boreal region of the
.16
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Northwest Territories. Replicate plots were used for
this study. Fertilizer and bacteria were applied with
the jbil. In fertilizer applied plots there was a rapid
increase in bacterial numbers. The saturates content of
fertilizer applied plots decreased with time. Treatment
of plots with oil degrading bacteria did not accelerate
the rate at which chemical changes in recovered oil oc-
curred. The reason given for this phenomenon was the
concentration of indigenous oil degrading bacteria in
these soils was high compared to the concentration of
bacteria introduced.
Two studies by Huddleston and Cresswell (1976) at
Billings, Montana and Ponca City, Oklahoma on degradation
of oily residues revealed degradation of oily residues
progressed, there was an increase in the percentage of
resin-asphaltenes, and a decrease in the percentage of
paraffins and aromatics. The Billings study showed that
70 percent of the applied oil was lost over an 18 month
period, with the percentage of resin-asphaltenes in the
remaining oil increasing from 20 to 60 percent. The
Ponca City study revealed a similar trend, with a 35
percent loss of applied oil occurring over a 24 month
period, and the percentage of resin-asphaltenes in the
remaining oil increasing.
Walker, Colwell and Petrakis (1976) studied the bio-
degradation rates of petroleum by monitoring the changes
in the concentrations of saturates, aromatics, resins and
asphaltenes over time. The results showed that the con-
centration of saturates decreased steadily, while the
concentration of resins and asphaltenes increased over
time. The aromatics concentrations decreased, leveled
off and then increased again.
Fate of Metals in Land Treatment of Oily Residues
Most of the land treatment studies have focused on
17
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short-term effects. Few researchers have evaluated the
potential for long-term impacts on the environment.
These impacts need to be addressed in view of the buildup
of £eavy metals in the soil during land treatment.
f V
Fuller (1977) reported that under anaerobic conditions
the mobility of several heavy metals (As, Cr, Fe, Cu, Zn)
is enhanced. (Anaerobic conditions can and do occur at
land treatment sites, particularly under conditions of
high soil moisture content, when leaching is most likely
to occur.)
Hahne and Kroontje (1973) reported that in the pres-
ence of chloride ion, the solubility of Cd, Zn, Pb, and
Hg is increased even at a pH of 9. They indicated that
at a pH of 9 soluble chloride complexes can be found at
ion concentrations of 354 and 28 ppm. High chloride ion
concentrations can be present at land treatment sites be-
cause of the occurrence of brines with crude oil and the
high chloride ion content of some wastes from refinery
operations.
Soils used for the disposal of oily sludges may con-
tain a number of heavy metals which are potentially toxic
to the environment. Contamination of ground water by
heavy metals is believed to be of minimal concern if ade-
quate soil pH is maintained at a land treatment site.
Most metals are immobilized when the soil pH is greater
than 6.5. The leaching of metals is therefore not of ma-
jor concern at treatment sites with proper pH control
(Dibble and Bartha 1979, Francsen 1980, and Huddleston
1979) .
Leeper (1978) believes that pH is the single most
important aspect of the reaction between heavy metals and
soils. Soil treated with sludges containing heavy metals
should be medium to fine textured, have a pH above 6.5
and contain 3-7 percent organic matter with a Cation
18
-------
Exchange Capacity (CEC) of at least 14 in order to be
considered acceptable for the retention of metals
(Huddleston 1979, Leeper 1978, Loehr 1979).
^ Hydrocarbon Processing (1980) reported that "vir-
tually all published information on landfarming indicated
that there is little migration of contaminants below the
top 30 cm (12 in) of soil". To date little work has been
done on leaching of metals in soil containing oil wastes,
although the movement of heavy metals in landfills or in
soils amended with sewage sludge has been studied exten-
sively (Schilesky, 1979). The possibility of heavy
metals leaching through soil is great if high pH levels
are not maintained at land treatment sites. Heavy metals
can be toxic, therefore, suitable oily wastes for land
treatment are those which do not contain extremely high
metal concentrations (Huddleston, 1979) .
Raymond, Hudson and Jamison (1976) conducted a land
treatment study in which oil degradation was monitored
over a one year period. The movement of lead, which was
the metal of highest concentration in the oil, was exam-
ined and no evidence was found that the nitric acid-
soluble form had leached through the soil. Dibble and
Bartha (1979) found hydrocarbons did not leach below a
depth at which oil sludge was mixed with sandy soil.
Based on Raymond et al.'s studies, Dibble and Bartha
concluded that heavy metal residues from oil sludges
would display low mobility in limed soil. Huddleston et
al., (1982) reported in a study carried out at five
closed refinery land treatment sites that wastes had been
degraded without appreciable migration of degradation
products, and that metals in the waste remained in the
application zone.
One problem that might arise from the disposal of
oily residues by land treatment is the movement of leach-
19
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ate through the unsaturated zone to the underlying ground
water, resulting in contamination of the ground water.
Thus^; the unsaturated zone at a land treatment site needs
to be monitored in order that any pollutant movement can
be detected. Current EPA regulations require the use of
GW monitoring wells, and the collection and analysis of
soil core samples as a method of detecting pollutant
movement. EPA has also required the use of soil moisture
samplers for sampling soil pore water in the unsaturated
zone under active land treatment sites.
Soil moisture samplers using a porous ceramic cup
have been used for many years for collecting soil pore
water samples. Briggs and McCall first reported on the
use of porous ceramic cups in 1904, and since that time,
their usage has increased considerably. However, with
their increased usage, questions have arisen as to the
validity of samples collected in this way.
Wagner (1962) used the porous ceramic cup and re-
ported no adsorptive capacity of the cup for nitrate
ions, but an appreciable adsorptive capacity of about 1
mg of N for NH. ions. Reeve and Doering (1965) used ce-
ramic cups to collect soil water samples for salinity de-
terminations. The values obtained from the sampler
agreed with the values obtained by the conventional satu-
ration method. They also found that the composition of
the sample changed with time, but that consistent and re-
liable values for the composition of the soil solution
were obtained when a vacuum in the range of 0 to 500 mil-
libars was used to collect the sample.
Grover and Lamborn (1970) reported that ceramic cups
contributed excessive amounts of Ca , Na and K to so-
lutions drawn through them, and adsorbed phosphorus from
solutions containing phosphorus. They found that leach-
ing the cups with 1 N HC1 reduced Na and K contamination,
20
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and the amount of phosphorus adsorbed, but appreciable
amounts of calcium contamination still occurred. Wood
(1973) also reported contamination of samples by Ca ,
Mg :> Na , HCO~ and Si02. He minimized the problem by
leaching the ceramic cups with 8 N HC1.
Zimmermann, Price and Montgomery (1978) reported
loss of nutrients after filtration through porous ceramic
cups used to sample sediment. The most significant loss-
es occurred with HN4 and P04~ ions. Levin and Jackson
(1977) also reported loss of NO ~-N when they used porous
ceramic cups for sampling soil water.
Johnson and Cartwright (1980) used soil moisture
samplers with porous ceramic cups for sampling the unsat-
urated zone under landfills in Illinois. They found that
samples taken with soil moisture samplers were represen-
tative of the surrounding leachate composition of major
ions. They pointed out that while sample variability or
bias of several milligrams per liter may be quite signif-
icant when the concentration of the ions of interest in
the soil water is low, this is not the case when sampling
highly contaminated leachate with high ionic concentra-
tions.
England (1974) pointed out the following:
(1) Concentrations and composition of the soil so-
lution are not homogeneous throughout its mass.
(2) Cations vary widely in the degree of dissocia-
tion from the surface of electronegative col-
loidal particles. Water drained from large
pores at low suctions may have a different
chemical composition from that extracted from
micropores.
(3) Concentrations of various ions in a soil solu-
tion generally do not vary inversely with the
soil water content. Dissolved quantities of
21
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some ions increase with increasing soil mois-
ture while quantities of other ions may de-
crease.
Hanson and Harris (1975), did extensive work on the use
of porous ceramic samplers. They found that the rate of
sample uptake was strongly influenced by cup uptake rate,
plugging of the cup, sampler depth, and the type of vacu-
um system used. They also found that a number of factors
affected the sample concentration as the sample was drawn
through the ceramic cup. These factors were intake rate,
leaching, sorption and screening.
Van der Ploeg and Beese (1977) showed that the soil
moisture sampler distorts the existing gradient patterns
in the soil in such a way, that around the ceramic cup
exaggerated percolation rates are created. They state
that the composition of the collected sample is not rep-
resentative for one particular depth, but reflects some
average composition of the surroundings. Van der Ploeg
and Beese found that extraction rates with even a small
vacuum applied, were much higher than the percolation
rate under freely vertically draining conditions. They
could find no relation between the amount of soil water
extracted and the freely percolating soil water.
A great deal of care must be taken in extrapolating
results obtained with the use of soil water samplers to
conditions which actually exist in the unsaturated zone.
This is especially true when dealing with environments
where solute concentrations are low. Little has been
written on the effect of the ceramic cups on low organic
concentrations which may be present in the soil water,
and this is an area which needs more research.
Despite these reservations, these samplers are cur-
rently one of the best methods of monitoring the movement
of pollutants in soil pore water at land treatment sites.
22
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They have a number of advantages:
(1) They can be installed under the active portion
of land treatment sites, and monitored off
; site.
(2) They are relatively inexpensive to install, and
do not require highly trained personnel to use
them.
(3) The sampler itself is inexpensive.
A soil moisture sampler commonly used in monitoring
the unsaturated zone is a pressure vacuum model which was
developed by Parizek and Lane (1970) . This sampler can
be effectively used up to depths of 50 feet, and can be
used to collect samples over a long period of time.
Volatile Emissions
A review of the literature dealing with land treat-
ment of oil residues did not reveal much information on
volatile organic emissions from the process. Three
sources, however, contained information about volatile
organic emissions from land treatment of refinery
sludges.
Minear et al. , (1981) conducted a study to assess
the atmospheric emissions from the land treatment of re-
finery sludges. This study was jointly funded by the
American Petroleum Institute and the U.S. Environmental
Protection Agency (EPA). These researchers developed a
small laboratory unit to simulate land treatment opera-
tions. The effects of certain variables on emission
rates such as sludge type, sludge volatility, soil mois-
ture content, wind speed, relative humidity, air tempera-
ture, soil temperature, sludge loading rate and the meth-
od of sludge application were studied. The authors found
that sludge volatility, sludge loading rate, application
method and soil moisture content were important parame-
23
-------
ters affecting emission rates. API separator and tank
bottom sludges were used in this study. The results of
this, study showed that the hydrocarbon concentration in
the ;air rose sharply during or shortly after sludge ap-
plications.
The concentration was at a maximum for less than
five minutes, and then decreased to a relatively low lev-
el within 30-36 minutes from the time of sludge applica-
tion. Sludges with different volatilities were used, and
the weight percent of applied sludge lost in 30 minutes
varied from 0.07 to 3.2, depending on the sludge.
Minear et al., found the addition of gasoline to the
sludge increased the emission rate, while water addition
had no effect on this rate. Subsurface injection and
delaying tilling for a while after application of sludge
were recommended as ways of minimizing emissions. Minear
et al., also showed that increasing soil moisture in-
creased the amount of hydrocarbons emitted, but heating
the sludge before application had no effect on the emis-
sion rate. Air velocity did not affect the total quan-
tity of hydrocarbons emitted, only the rate of emission.
Francke and Clark (1978) conducted land farming ex-
periments at Oak Ridge National Laboratory to evaluate a
biological assimilatory process for disposal of waste oil
and machine coolant. They applied oil and fertilizer to
a 0.005 hectare (0.088 acre) plot, tilled to a depth of
15 cm (6 in) and cultivated regularly for 4 months. Av-
erage oil application rate was 0.154 liters per cubic me-
ter (1.15 gallons per cubic foot) of soil. Decomposition
rate of oily waste was reported to be 24 kg/m (1.5 Ib
per cubic foot) of soil per month; decomposition rate of
coolant was reported to be 71 kg/m /month (4.45 Ib/ft
month).
They also conducted laboratory tests to determine
24
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the hydrocarbon evaporation rate from the test plots.
Total evaporative losses from actual test plots over the
53 d,ay test period were calculated to be about 31.8 li-
ters- (8.4 gallons), equivalent to less than 0.1 percent
of the total oil applied.
Laboratory tests were also conducted to determine
the evaporation rate from the machine coolant. Estimated
losses during the 78 day test period were 110-140 liters
(29-37 gallons) , less than 0.6 percent of the total oil
applied. The author reported that the primary evapora-
tive constituents were those identified with oils and
coolants.
Volatile Organic Compound (VOC) emissions from a
land treatment operation of petroleum sludge were studied
by the Suntech group (undated). API separator sludge
containing about 5 weight percent oil, and centrifuge
sludge containing about 8 weight percent oil were land-
treated.
Centrifuge sludge was spread and tilled and volatile
organics were measured during a 13 day period. Volatile
organic compound emissions averaged about 594 kg/ha (530
pounds) of hexane equivalent per acre, or approximately
46 kg/hectare/day (41 pounds per acre per day) . Total
emissions were reported to be about two weight percent of
the oil applied.
Spreading of API separator sludge resulted in VOC
emissions of 2196 kg of hexane equivalent/hectare (1960
pounds per acre), or 85 kg/ha/day (76 pounds per acre per
day) which represented about 11 weight percent of the oil
spread. Tilling after spreading increased VOC emissions
to 2357 kg/ha (2103 pounds per acre), or about 14 weight
percent of the oil spread.
Tilling and high temperature increased the emission
rates from both types of sludges. Tilling was not a
25
-------
factor over an extended period, although it initially
increased emissions.
,-Stearn, Ross and Morrison (1977) conducted a litera-
ture-review relating to oily waste decomposition, vola-
tilization, migration through soils, and interaction with
the environment when oily waste was disposed on land.
Four case studies were performed to determine if the
method was practical and environmentally acceptable.
The results of this review showed that the degree of
oil loss by volatilization is related to the vapor pres-
sure of hydrocarbons, soil porosity, tortuosity and sur-
face absorption characteristics of the soil. Hydro-
carbons with high vapor pressures, such as propane, evap-
orate before outward migration or biological oxidation
occurs in soils. However, lower vapor pressure hydro-
carbons, such as heavy oils, residual fuel oils, grease,
solid paraffins and high molecular weight asphaltenes;
migrate or biologically oxidize before evaporation.
Using information from the literature, the authors es-
timated that for highly volatile hydrocarbons deposited
in soil to a concentration of 0.1 g/cm , it would require
approximately one month for all oil in the top 4.6 cm
(1.8 in) layer to evaporate. Further, for a heavier fuel
oil, with a contamination zone depth of 9.8 inches, ap-
proximately 6 percent of the oil would evaporate in two
years. The range of time constants relevant to biologi-
cal oxidation of oil is estimated between two and twenty
months. Therefore, the oil evaporation rate is insignif-
icant as compared to the biological oxidation rate.
The authors reported that relative amounts of evap-
orated versus biologically oxidized oil can be affected
by the disposal methods employed. For any hydrocarbon
having a vapor pressure less than 100 mm of mercury, the
ratio of evaporation to biological oxidation can be
26
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minimized by maximizing the depth of plowed zone if the
soil is not completely saturated with water. Although
this.' procedure will decrease the biological degradation
rate>,,it will decrease the evaporation rate even more.
Chamber techniques to measure the gas transfer
across the soil-atmosphere interface have received con-
siderable emphasis the past few years. Matthias,
Blackmer and Bremner (1980) described a chamber technique
for field measurement of emissions of nitrous oxide from
soil. The researchers placed an insulated cylindrical
metal chamber (diameter 88 cm; height 17 cm) over the
soil surface for 20 minutes and collected air samples in
1 liter evacuated glass bottles fitted with glass stop-
cock in 5 minute intervals. A rotary valve pump was used
to evacuate each sample bottle to a pressure of <.l mm
Hg. A windbreak was used to minimize wind-induced move-
ment.
The air samples then were analyzed for nitrous oxide
(N_0) within 24 hours by a gas chromatographic procedure.
The rate of nitrous oxide emission was calculated from
the increase in the concentration of nitrous oxide in the
air within the chamber.
The effects of wind break, insulation, air pressure
fluctuation and mixing air within the chamber were
studied. The authors reported that the concentration of
nitrous oxide in air within the chamber increased linear-
ly with time on calm day; however, it did not increase
linearly with time on windy days. The effect of insula-
tion showed that the temperature perturbation of air
within the insulated metal chamber was very small com-
pared with the perturbation observed within the metal and
plexiglass chambers. Since temperature has a very sig-
nificant effect on the rate of microbial activity and the
resulting nitrous oxide emission from the soil, extensive
27
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tests showed that the above described chamber would not
significantly affect the soil temperature.
_'The authors used an electric fan to mix the air
within the chamber. The repeated tests revealed that
there was no significant difference between results ob-
tained with and without using a fan.
Studies by Kimball and Lemon (1971-1972), have shown
that air-pressure fluctuations caused by turbulent move-
ment of air over the soil surface may affect gaseous mass
flow within the soil. However, Matthias et al., (1980)
reported that air-pressure fluctuation induced by with-
drawing and reinjecting air over the soil did not signif-
icantly affect the rates of N_0 emission at various sites
using the chamber technique. According to Matthias, the
chamber technique has the important advantage of not sig-
nificantly disturbing the structure or the environment of
the soil under study.
28
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SECTION 4
DESIGN AND OPERATION OF THE LAND TREATMENT SITE
SITE SELECTION
The ten acre site selected for this study is located
on university property adjacent to the east right-of-way
of Interstate Highway 35 and immediately north of
Westheimer Field, the University Airport. More specif-
ically, it is located in the Southwest quarter, of the
Northeast quarter, of Section 14, Township 9 North, Range
3 West, Cleveland County, Oklahoma. Figure 4.1 shows the
location of the site. The site is owned by the Univer-
sity of Oklahoma. The climatic conditions in this area
can be described as mild winters and hot summers. The
winters and springs during the period of the project were
unusual in that rainfall was significantly above average
for the duration of the project.
The following criteria represent the major consid-
erations in selecting the location of the research site:
* The site should be owned by the University of
Oklahoma.
* The site could have no past history of oil ap-
plications.
* A long term commitment of the site for use in
research must be available.
* The site should be remotely located relative to
urban population.
* The surface slopes should be mild to prevent
erosion but at least 1 percent to provide
29
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i i
B E
14
LAND
.TREATMENT
RESEARCH
//o
UNIVERSITY pF'OKLAHOMA
RESEARCH PAf K
v r
Figure 4.1. Land treatment research site location.
30
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proper drainage.
* An impermeable clay should underly the site and
maximum vertical separation from any fresh wa-
;; ter aquifer must be provided.
* The surface soils should represent good agri-
cutural soils with lateral uniformity.
* Reasonable road access and economic access to
water and electric utilities is needed.
The site selected could not be directly serviced with a
water supply without great expense. With this exception
the research site meets all of the above criteria.
SITE DESCRIPTION AND CHARACTERISTICS
The Cleveland County Soil Survey defines the surface
soils at the site to be part of the Bethany Silt Loam se-
ries. A reprint of the survey description of this soil
series is as follows (Soil Conservation Service, 1960) :
Bethany silt loam, (Bb)
This dark deep noncalcareous soil of the prairies is
not extensive but occupies a few fairly large areas
totalling 15,200 acres northwest of Norman. Surface and
internal drainage are both very slow, but the soil is ad-
equately drained for all crops commonly grown. It has a
high water holding capacity and absorbs most of the pre-
cipitation, but crops are sometimes damaged during long
droughts. One reason is that plants are unable to obtain
water fast enough from the clay in the lower subsoil lay-
ers when the soil moisture content is low. Slope is less
than 1 percent, therefore erosion is not a problem.
The surface soil, to a depth of about 38 cm (15 in),
is a dark grayish-brown or dark-brown granular slightly
acid silt loam that tends to crust on drying but is easi-
ly kept loose and granular under a wide range of moisture
condition. The surface soil grades into the upper sub-
31
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soil, a dark-brown or grayish-brown porous granular soil
soil of slightly acid silty clay loam. This upper sub-
soil., 10 to 20 cm (4 to 8 in) thick, is neither tight nor
hard~> even when extremely 'dry, and is easily penetrated
by moisture, air and plant .roots. The upper subsoil
grades into a lower subsoil of brown firm blocky clay
that continues with little change to depths of 102 to 127
cm (40 to 50 in). Next in profile is brown heavy noncal-
careous clay mottled with yellow and reddish brown, which
grades at depths of 183 to 244 cm (6 to 8 ft) into alka-
line to calcareous reddish silty clay or silty shale.
This shale may be residuum of ancient water-laid materi-
als.
Soil Analysis
Composite samples of the top eight 20 cm (8 in) of
soil from the site were collected for gradation analysis.
Samples were collected in a manner to establish variation
in gradation of surface soils across the site. Gradation
analysis were performed in accordance with AASHTO T88-72,
Standard Method for Particle Size Analysis of Soils which
includes hydrometer analyses for the fine soil particles.
Results of the analyses are presented in Table 4.1.
TABLE 4.1. GRADATION ANALYSIS OF SURFACE SITE SOILS
General Description of
Sample Relative to the
South 1/2 of Site
1-A-East 1/2
1-B-East 1/2 (1-A split)
2-A-East 1/2
3-A-West 1/2
Average Results
Sample
Depth
(cm)
20
20
20
20
%
Sand
4.5
3.7
3.9
4.3
4.1
%
Silt
78.0
79.3
78.6
77.2
78.3
%
Clay
17.5
17.0
17.5
18.5
17.6
Textural
Classif-
ication
Silty Loam
Silty Loam
Silty Loam
Silty Loam
Silty Loam
32
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The maximum variation found is within the limits of
analysis error and indicates that the surface soil in the
research area is of uniform texture. The top 12 inches
of surface soil is of primary interest, as it represents
the zone of incorporation for the land treatment process.
The samples described in Table 4.1 were further an-
alyzed to determine their maximum densities at optimum
moisture content and their plasticity characteristics.
The "Harvard Miniature" procedure was used in the density
measurements. The liquid limit test was conducted in ac-
cordance with AASHTO T89-76, Standard Method for Deter-
mining the Liquid Limit of Soils. Plastic limit and
plasticity index procedures as . described in AASHTO
T90-70, Standard Method for Determining the Plastic Limit
and Plasticity Index of Soils was followed. Results of
these tests appear in Tables 4.2 and 4.3 below.
Uniformity of the surface soils on the site is fur-
ther established by the low variation in the density and
plasticity data. This soil is plastic over a small range
of moisture contents (Table 4.3) indicative of the high
silt and relatively low clay content of the surface soil.
TABLE 4.2. DRY DENSITY - OPTIMUM MOISTURE
ANALYSIS RESULTS
Sample Sample
Identifi- Depth
cation (cm)
2-A 0-20
3-A 0-20
Average Results
Maximum Optimum
Dry Density Moisture Content
(PCF) (%)
107
108
107
.5
.0
.7
15
14
14
.5
33
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TABLE 4.3. PLASTICITY ANALYSES
Idenjbifi- Sample " Liquid
cation Depth Limit
.; :; (cm) (%Moisture)
1-A
1-B
2-A
3 -A
Average
0-20
0-20
0-20
0-20
Results
23.0
23.7
24.1
23.9
23.7
Plastic
Limit
(%Moisture)
21.5
21.0
20.0
20.8
20.8
Plasticity
Index
(%Moisture)
1.5
2.7
4.1
3.1
2.9
Several shallow soil cores, approximately five feet
deep were taken across the site. In addition, shavings
from four deep site cores air drilled to 30.5 m (100 ft)
were examined. Inspection of deep core materials further
indicated that uniformity exists in the underlying
strata. A general description of the typical soil pro-
file beneath the site is given in Figure 4.2.
Clay material underlying the silty loam on the
surface was found to have a coefficient of permeability
less than 10~ cm/sec. Underlying clay gradually changes
to red clay shale at approximately sixty inches. Red
shale continues to 30.5 m (100 ft) where drilling ceased.
Thin lenses of sandstone 3 to 5 cm (1 to 2 in) were en-
countered at various positions in the shale beds.
No ground water table was encountered in any of the
deep core holes. Known area hydrogeology indicates the
only major aquifer water table to be approximately 154 m
(500 ft) deep or deeper in the vicinity of the site (25).
The soil pH ranged from 6.5 - 8.5.
SITE DESIGN AND CONSTRUCTION
The site was designed to hold a maximum of 50 plots,
2.7mx6m (9 ft x 20 ft) . Twenty foot buffer zones
34
-------
Depth
(m)
Ground Surface
5 -
30.5
Silty Loam
Grey to Black Clay
Red Clay Shale with
Thin Interbedded
Sandstone Lenses
No Groundwater Table
Encountered
Limit of Investigation
30.5
Figure 4.2. Typical vertical soil profile
at site.
35
-------
were provided between plots to minimize material trans-
fer between plots. This spacing also made it convenient
to maneuver the tractor, tiller, and applicator to each
plot'.
- - The entire site was diked to prevent surface water
run-on to and run-off from the active site. A retention
pond designed to retain run-off from a twenty-five year,
twenty-four hour storm was constructed inside the diked
area. Figure 4.3 shows the layout of the land treatment
facility. Four ground water monitoring wells were in-
stalled; one upgradient, and three downgradient of the
ground water flow. The ground water flow in this loca-
tion is from east to west. Each well was 30.5 m (100 ft)
deep.
The site was equipped with two tanks for storage of
oil refinery sludges with a total capacity of 45,420 1
(12,000 gallon). A mixer was mounted on top of one of
the tanks to provide uniform mixing of the waste before
application. Contents of the other tank were pumped to
the mixed equipped tank prior to application.
Sludge Application
Sludges were applied to the plots with an applicator
attached to a 750 1 tank equipped with a 5 hp gasoline
engine powered pump. The applicator were designed and
constructed by University of Oklahoma personnel, consist-
ed of a 2.7 m (9 ft) manifold with six spray nozzels
equally spaced to assure uniform applications. A 1/2 hp
motor drove the manifold along a 20 ft frame (Figure
4.4). One pass of the manifold applied sludge uniformly
to the entire 6 m x 2.7 m (20 ft x 9 ft) plot. The
amount of oil applied to each plot was controlled by the
number of passes. Before each application the plots were
tilled, and the applicator calibrated.
36
-------
Figure 4.3. Partial view of land treatment facility
. 37
-------
Figure 4.4. Sludge applicator.
38
-------
Tilling was performed using a John Deere 850 tractor
and a 1.5 m (5 ft) rototiller. After application the
plots were immediately tilled twice to ensure uniform
mixing of the oily sludge in the zone of incorporation.
T »
Design till zone depth was 30 cm (12 in).
Process Control Consideration
The objectives of this study were to determine the con-
trolling factors for land treatment of refinery residues
and to optimize these factors for design purposes. Fac-
tors widely identified as controlling the land treatment
process for oily sludges are:
(1) Relative composition of the organic fraction of
the sludge;
(2) Temperature;
(3) Water;
(4) Nutrients;
(5) pH; and
(6) Oxygen availability.
Although these factors are important and were monitored
or controlled in this study, they were not the main fac-
tors emphasized. The primary factors were loading rates,
loading frequencies and tilling.
For the purpose of this study, the first three fac-
tors mentioned above were monitored but not controlled.
The relative concentration of various fractions of oil in
the sludge was dictated by process conditions in the re-
finery. Temperature and water are climatic factors which
were allowed to vary naturally. Although moisture con-
ditions can be partially controlled by extensive drainage
systems and by irrigation; the decision made by the re-
searcher, supported by EPA personnel, was to operate the
system under natural climatic and moisture conditions.
Nutrients and pH can be controlled to a large extent
39
-------
by the addition of fertilizers and lime. The soil pH is
an important parameter for biodegradation, and also for
immobilization on the heavy metals found in the sludge.
Nutrients are required for the biological processes to
proceed efficiently. Routine monitoring of pH and ni-
trate nitrogen was performed as discussed in the results
section of this report. In addition, the concentration
of chloride ion was monitored.
The availability of oxygen throughout the zone of
incorporation is extremely important for bio-oxidation of
the organic materials. Oxygen availability is a function
of tilling, loading rates and moisture content. The oxy-
gen was primarily controlled in this project by cultiva-
tion or tilling the zone of incorporation. Proper mixing
and aeration of the soil in the zone of incorporation is
an integral part of the land treatment process. The
function of tilling is analagous .to the function of
aeration in an activated sludge wastewater treatment pro-
cess; it provides mixing and aeration of the residue-
laden soil.
A relatively large amount of information exists on
the soil-water relationship as it impacts common
agriculture practices such as field preparation, crop
cultivation, erosion management, etc. In contrast, very
little information is available regarding moisture rela-
tionships of soils to which oil sludges have been ap-
plied. In the land treatment of oily sludge, the com-
plexity of soil-water relationships is increased by the
addition of oil. In fact, the effects of various frac-
tions of oil, oil-water emulsions, and other matrix in-
teractions make thorough understanding of factors rele-
vant to the soil tilling process very difficult. It was
beyond the scope of this study to explore in-depth the
complex relationships of oil, water, and soil in the zone
40
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of incorporation.
Experimental Design
.-The original experimental plan called for a 4 x 4
factorial design with oil loading rate and application
frequency as the treatment parameters. Four values of
loading rate and loading frequency were selected to cover
the range of practical loading conditions. Replicates of
each combination were to be used for increased statis-
tical significance.
The first application to the plots occurred in Au-
gust 1981. For this application the loading rates of oil
were 3, 5, 9, and 13 percent (soil dry weight basis),
with application frequencies of 1, 6, 12, and 18 applica-
tions per year. During the August 1981 application the
high rate - low frequency plots could not be fully load-
ed, due to the constraint imposed by the field capacity
of the soils. Even duplicate plots could not be loaded
to the same level because of varying antecedent soil
conditions. Thus, several plots only received a fraction
of the nominal loading. It was intended to apply the
total planned quantities within a few days to simulate a
single loading of the plot.
However, immediately following the first applica-
tion, heavy rains prevented further tilling, application,
and sampling until January 1982.
Since the original plan could no longer be followed,
a change was made in the nominal treatment loading rates
and frequencies. Once again, several of the high rate -
low frequency plots could not be fully loaded at the
nominal rate. Although many attempts were made until
November 1982 to maintain the schedule, the actual
loading rates and frequencies did not correspond to the
planned treatments. A third treatment schedule was then
41
-------
developed, and new plots added so that high rate - low
frequency plots could be evaluated.
;Weather conditions continued to plague the project,
forcing application, tilling, and sampling as weather
permitted. The amount of sludge and time of application
was recorded for each plot.
A compilation of oil loadings (as percent of dry
soil weight) given to each plot is presented in Table
A.I, Appendix A. These tables give date of loading,
elapsed time since the first sludge application, and the
amount of oil applied as a percent of dry soil weight.
A comparison of total cumulative oil loadings for
each plot is given in Table 4.4. Using total loading as
a criterion for replicate comparison, only six total
loadings were replicated. Of the six sets of total load-
ing replicates only four sets of plots are actually true
replicates which were loaded the same amounts on the same
dates. The other plots, though applied with the same
cumulative amount of oil, were not loaded on the same
days and therefore, cannot be considered true replicates.
Tilling
One objective of this study was to evaluate the op-
timum tilling frequency. It was originally intended to
perform an experiment using several plots which had re-
ceived the same oil loading, with tilling frequency as
the process variable and oil loss rate as the criteria
for evaluation.
Following the initiation of the oil loading it be-
came evident that wet field conditions precluded opera-
tion of the rototiller and tractor, thus, imposing a
rigid tilling schedule without regard to field conditions
and soil-oil-water relationships was neither practical
nor desirable. When attempts were made to till plots
42
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TABLE 4.4. TOTAL CUMULATIVE OIL LOADINGS - 1981, 1982
Plot
No.
1
2
4
5
6
7
8
9
10
11
13
14
15
16
17
18
20
21
22
23
24
25
26
28
29
30
31
32
34
35
36
38
Total Loading
% Oil (dwb) *
20.04
10.79
4.15
14.88
22.54
8.53
26.50
5.49
14.76
8.53
9.20
3.74
14.76
10.35
8.63
2.78
14.30
22.81
22.43
21.68
7.48
2.21
12.04
24.23
22.50
14.20
8.63
4.92
8.24
18.71
12.56
7.48
* dwb = soil dry weight basis
43
-------
which were wet, it was difficult to control tilling depth
and preserve plot boundary dimensions. Deepening the
zone." of incorporation and lateral enlargement of plots
was :.!to be avoided so that the computation of mass bal-
ances would not be influenced.
As discussed above, the research site was designed
with an approximately 1 percent slope from west to east
to allow surface run-off to flow overland to a retention
pond. Though the surface drainage between plots was
adequate, the test plots themselves were poorly drained.
Tilling operations in the zone of incorporation increased
the volume of pore space within the soil matrix. Thus,
each plot behaved like a sponge surrounded by relatively
impermeable undisturbed soil.
Water loss from the soil may be slowed by the pre-
sence of oil. Meyers and Huddleston (1979) suggested
that oil addition increases the hydrophobic properties of
agricultural soils. Whether persistence of excess soil
moisture in test plots was the result of increased mois-
ture holding capacity or the result of physical contain-
ment due to the physical configuration of the plots is
not known.
During wet conditions, soil in the zone of incor-
poration had a 'pudding-like1 consistency with a moisture
content above and at time's above the liquid limit, above
the field capacity. After a period of drying, the plots
would appear dry and crusty on the surface; however, be-
neath this 2-4 cm crust, the plots remained wet. As a
rule of thumb, if a stake could be easily inserted into
the plot by hand, the plot was too wet to till.
Once the plots had dried sufficient for operation of
the tilling equipment, they were tilled several times to
speed the drying process. Tilling the soil in a plastic
condition tended to form clumps of approximately 10 cm (4
44
-------
in) diameter, and further tilling did not appreciably
reduce this size.
.-The agglomerated clumps in the zone of incorporation
created a condition of large void spaces within the
tilled depth. The cohesion of the soil in these clumps
increased dramatically upon further drying. Examination
of cross-sections of these clumps revealed low macro-pore
space volume, thus, oxygenation was occurring only at the
outer surface. Tilling of the dried clumps did not sig-
nificantly reduce their size but only rearranged them.
In addition, resistance of the clumps to the shearing ac-
tion of the rototiller made tilling to the required depth
difficult.
Inclimate weather made it impossible to maintain the
loading rates and frequencies established in the original
design, and to till the plots as desired. Limited til-
ling hampered sampling efforts, leading to a somewhat ir-
regular pattern of sampling. For most of the study, sam-
pling dates closely corresponded to application dates.
Zone of incorporation soil samples were typically ob-
tained prior to each sludge application, with other types
of samples such as deep cores obtained on a more infre-
quent basis. In some cases, plots were sampled more than
once between applications, especially if oil was applied
on a low frequency basis.
In an effort to improve the precision and accuracy
of oil content measurements, sampling and analytical
methodology constantly evolved throughout the first year
of the project. The sample preparation and analysis
methods developed during this period are located in
Section 5.
45
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SECTION 5
PROCEDURES
SAMPLING METHODS
Soil Sampling
Sampling is one .of the most important steps in data
collection and analysis. A representative sample must be
obtained in order to obtain consistent and meaningful re-
sults. Studies were performed to establish a sampling
method.
The initial sampling method consisted of a single
sample from each plot using a 2.54 cm (1 in) Shelby tube.
Analysis of the data showed that based upon the amount of
oil applied to each plot effective oil recoveries and
consistent results were not obtained. The second method
consisted of obtaining five samples from each plot; each
sample consisting of a composite of twenty 2.54 cm (1 in)
in diameter, 0.3 m (1 ft) long Shelby tube cores. The
high variability resulting from this method was attri-
buted to the diameter of the Shelby tube being less than
the maximum diameter of a significant portion of the ag-
glomerated particles.
In order to reduce the variability, two other meth-
ods of sampling were studied. One consisted of using a
8.9 cm (3.5 in) diameter sampling tube and obtaining
three cores randomly across the site per composite sample
and taking three samples per plot. The second method
consisted of using a 4.8 cm (1.9 in) sampling tube,
46
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obtaining 10 cores randomly per composite sample and 3
samples per plot. Statistically, in analyzing the data
obtained from these two sampling methods, the method
using -.the 4.8 cm (1.9 in) sampler gave less variation in
the analyses than the 8.9 cm (3.5 in) diameter sampler.
Hence, the method using the 4.8 cm (1.9 in) sampler was
selected. Table 5.1 shows the variations in the samp-
ling methods.
Ground Water Sampling
Samples from the four monitoring wells were obtained
using a 5 cm (2 in) diameter Kemmerer sampler. The
sampler consisted of a 0.94 m (3 ft) long stainless steel
cylinder with Teflon caps on both ends suspended by a 61
m (200 ft) nylon cord. Samples were collected in 500 ml
glass bottles prewashed with soap solution and organic
free water as outlined by EPA procedures.
Soil Moisture Sampling
The soil water passing through the unsaturated zone
beneath the zone of incorporation was also sampled.
Sampling of the soil pore water was accomplished by in-
stalling soil moisture samplers (lysimeters) at a depth
of approximately 1.2 m (4 ft) at the site. The sampler
used was Model 1920, sold by Soil Moisture Incorporation
of California. It was installed according to the follow-
ing procedure.
A 10 cm (4 in) hole was drilled to the required
depth, and thoroughly cleaned out, making sure that the
hole was not contaminated with soil from the zone of in-
corporation. The bottom of the hole was tamped, and the
sampler was seated in 300 mesh-silica sand, so that the
ceramic cup of the sampler was completely covered. Par-
ent soil (15 cm) was placed back in the hole, and tightly
tamped. A layer of dry bentonite clay was then placed in
47
-------
00
TABLE 5.1. STATISTICAL ANALYSIS FOR CHOICE OF SAMPLER
Sample % Oil
Mean
Deviation SS
»
':-. >°F
Medium Sampler (1 7/8" dia.)
6-1-1
6-1-2
6-1-3
6-2-1
6-2-2
6-2-3
6-3-1
6-3-2
6-3-3
Large
6-1-1
6-1-2
6-1-3
6-2-1
6-2-2
6-2-3
6-3-1
6-3-2
6-3-3
8.4834
8.4250
8.5362
SS = 0.245244
8.3975
8.2848
8.5787
7.9491
7.8668
7.7241
0.012680 EMS analysis
Sampler (3" dia.)
6.9641
6.3943
7.7072
SS = 0.103262
8.9178
8.0809
8.5516
8.1635
8.3353
7.6881
8.4815
(0.2320)
MSS = 0.122622
8.4203
(0.1708)
7.8467
(-0.4028)
8.2495
7.0219
MSS = 0.103262
8.5168
(0.2272)
8.0623
(-0.2273)
7.8670
0.00187
-0.05653 0.006188
0.05467
-0.02283
-0.13553 0.043971
0.15337
0.10243
0.02013 0.025921
-0.12257
ESS 0.076030
-0.05777
-0.62757 0.866857
0.68533
0.40103
-0.43587 0.352021
0.03453
0.10120
0.27300 0.224796
ESS 1.443676
2
2
2
6
2
2
2
6
0.240613 EMS analysis
-------
the hole followed by more parent soil. The hole was
filled to about 20 cm (8 in) from the top with parent
soil:, which was added in small amounts and tightly
tamped. Another layer of 5-8 cm (2-3 in) of dry
bentonite clay was then added and the hole filled with
soil. Figure 5.1 is a diagram of the mode of instal-
lation.
The principle involved in the operation of a lysi-
meter is that a vacuum is applied to the suction side of
the tubing as shown in Figure 5.2. Vacuum is displaced
by moisture entering in through the porous cup at the
bottom of the lysimeter tube. Initially the water
saturates the pores of the ceramic cup and then water
flows into the cup due to the vacuum applied. The sample
is collected from the ceramic cup by applying a positive
pressure thereby displacing the water.
Sludge Sampling
Sludge samples were obtained from the storage tanks
by lowering a 500 ml sampling bottle into the tank and
retrieving a sample. Prior to sampling, the mixer was
turned on for approximately 12 hours to insure complete
mixing of the tank contents.
Air Sampling for Volatile Organics
Methodology for sampling volatile organics from land
treatment sites was not available; therefore, the first
quarter of this project was devoted to developing metho-
dology for reliably sampling and accurately analyzing
volatile compounds being emitted to the atmosphere from
land treatment of petroleum sludge. Laboratory and field
studies were performed to determine the effects of load-
ing rates and frequencies, air and soil temperature, soil
moisture content, relative humidity and sludge volatility
on the magnitude and rates of volatile organic losses.
49
-------
Access tubes
Bentonite clay
Ground surface
Soil moisture sampler
Silica sand 300 Mesh
Figure 5.1. Method of installation of soil
pore water sampler.
50
-------
2-WAY PUMP
,.
VACUUM PORT AND GAUGE'
PRESSURE VACUUM IN
BKNTONITE
DISCHARGE TUBE
PLASTIC TUBING
PLASTIC PIPE 24" LONG
BACKFILL
SILCA SAND *^_!?»v:;.v:
. - . fi^
POHOUS CUP
AMPLE BOTTLE
Figure 5.2. Vacuum soil moisture sampler.
-------
ANALYTICAL ANALYSIS
Simulation Equipment for Air Sampling
;;^ simple system for the measurement of the rate of
emission of volatile hydrocarbons resulting from the land
treatment operation of petroleum oily sludge was designed
and constructed. Flexibility, simplicity, reliability,
portability and durability were features sought in the
design of the monitoring and collection system. Figures
5.3 and 5.4 depict the simulation apparatus used in the
field and laboratory, respectively. Figure 5.5 shows the
physical arrangement of the apparatus in the field.
This design incorporated an insulated, rectangular,
open bottom chamber fabricated from aluminum with a
length of 41 cm (11 in), a width of 14.6 cm (5.7 in) and
a height of 29 cm (11.4 in). It was insulated with 4 cm
(1.6 in) of styrofoam. The bottom of the chamber circum-
2 2
scribed an area of'0.07 m (0.78 ft ). The following ac-
cessories were provided:
1. A small variable speed AC fan was installed on
the top of the chamber to mix the air within
the chamber.
2. Two dial thermometers were inserted through
ports to record air and soil temperature inside
the chamber.
3. A dew point hygrometer was used to measure va-
por pressure and relative humidity inside the
chamber.
4. A port through which breathing quality com-
pressed air was provided to transport pollu-
tants from the sampling chamber to the hydro-
carbon detector and columns packed with appro-
priate adsorbents. Air flow rate was con-
trolled with a regulator equipped with a flow
meter.
52
-------
Samp too
>ump
Sample
Concentrator
Vafca
I Valve
Ports to
Insert Thermometer
Port To Bleed -w
Oil Excess Air O
0
Hydrocarbon and
Molaluro Trap
Fan Motor
Tharmomalara
O
TLV Snllfer
Daw Point Hygrometer
Compressed Air
Figure 5.3. Land treatment simulation apparatus
used in the field.
-------
TLV SnHlar
01
Pump
Sampla
Concantrator
Prasaura Gauge
Compreeaed Air
Valva
Valve
f Port To Bleed
' Oft Enceea Air O
CB
mg
-t-^
& ?
f
(
^\
Ports To
Inaart Themometera
Dew Point Hygrometer
Preaeura \v >
Gauge *- ^^^
Monitoring Chamber
Sprayer Tank
Figure 5.4. Land treatment simulation
apparatus used in the lab.
-------
-
Figure 5.5.
Air monitoring equipment set up
in the field.
55
-------
5. Ports were provided on the opposite end of the
chamber from the inlet port, to monitor total
volatile hydrocarbon by a Bacharach Instrument
.-.. :; Co. TLV Sniffer and to concentrate volatile
compounds on an appropriate adsorbent material.
6. A sprayer consisting of a two-gallon, polished
stainless steel tank, with removable syphon
tube, hose adaptor and discharge unit was at-
tached to a fan pattern nozzle inside the cham-
ber to distribute the sludge evenly over the
soil surface.
7. The inside of the chamber was coated with epoxy
paint to eliminate contamination from the alu-
minum.
8. To insure a good seal between the chamber and
the soil surface, an aluminum band 3.8 cm (1.5
in) in depth was extended from the bottom
edge of the box and embedded in the soil.
Preparation of Equipment for Sampling
The TLV Sniffer, used for monitoring total volatile
hydrocarbons, was calibrated with hexane; calibration was
checked with known concentrations of hexane before and
after each run.
A MDA scientific accuhaler model 808 personal samp-
ling pump, used for collecting volatiles in adsorbent
tubes, was also calibrated before and after sampling
using a soap bubble flow meter. Flow rate through the
trap was 30 to 31 ml/min.
The hygrometer probes were dried in a 60-80°C (140-
180°F) oven for about 1/2 hour to remove excess moisture
before using.
Field Sampling Protocol and Procedure
After the measurement methodology was developed and
56
-------
equipment was tested and calibrated in the laboratory,
field studies were conducted at the research site. Oil
was --applied to the soil surface at five loading rates,
with;: .varying frequencies.
The procedure for using the chamber involved placing
it over the plot and inserting it into the soil to a
depth of 3.8 cm (1.5 in). Meanwhile, the air control
valve was opened to maintain the desired air flow rate
and the head-space fan was turned on. To allow equilib-
ration, the dew point hygrometer was turned on at least
10 minutes before sampling. The hygrometer probes were
inserted into the chamber through two scalable ports on
the top surface of the chamber.
Soil and air temperatures were determined by dial
thermometers (range -40 to 71°C). The temperature of the
air within the chamber was measured at 6.4 cm (2.5 in)
above ground level. The temperature of air outside the
chamber was also measured at the same height. The temp-
eratures of soil inside and outside the chamber were
measured at a depth of 5 cm (2 in) below ground level.
Samples were taken using the TLV Sniffer and solid
sorbent tubes.
The Sniffer was purged for at least 10 minutes prior
to sampling. It was then zeroed with ambient air prior
to sampling. The Sniffer probe was connected to the
brass quick connect (Figures 5.2 and 5.3) valve in one
side of the chamber. The total volatile hydrocarbon
concentration in the air leaving the chamber was then
monitored with the Sniffer until equilibrium concen-
tration was reached. Samples were collected according to
the predetermined sampling schedule. The sampling
schedule was adjusted to take into consideration
abnormalities in the field. The resulting sampling
schedule was determined by the concentration vs time
57
-------
curve which was the product of many experiments.
To determine the identity and relative quantity of
organic pollutants, sampling was also performed by draw-
ing-exiting air through a 0.64 cm (2.5 in) (outside dia-
meter) stainless steel trap packed with 7.6 cm (3 in) of
Tenax-GC (60/80) and 2.54 cm (1 in) of silica gel (100/
200). Figure 5.6 shows the sampling cartridge.
Tenax-GC, a typical sorbent for collecting volatile
compounds at room temperature, is a porous polymer that
is based on 2,6-diphenyl-p-phenylene oxide. However,
many of the lighter organic compounds are not adequately
retained at room temperature by Tenax-GC (Bertsch et
al., 1974). By using the cryogenic method, in addition
Glass Wool
i i ,
Tanax G C Silica Gal
Olmanaiona: 4 In. by .25In. 0.0. Stalnlata Slaal Tube
5
Figure 5.6. Sample concentrator.
to increasing the efficiency of collecting low molecular
weight hydrocarbons (C2-C6^ (Singh, 1980; Bertsch et al.,
1980? Seifert and Ullrich, 1978; Altschuller, et al.,
1971; Hodren et al., 1979), the oxidation or polymeri-
zation of constituents is minimized (Singh, 1980).
Nevertheless, cryogenic trapping was dismissed due to
difficulty of using this system in the field.
Pellizzari (1974, 1975) developed an analytical
technique to determine the collection efficiency of many
sorbents, including Tenax-GC, during the concentration of
58
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hazardous vapors from a moving air stream. He reported
that Tenax-GC was greater than 90 percent efficient in
trapping hazardous vapors.
^'Silica gel exhibits a great selectivity among atmos-
pheric gaseous and vaporous constituents. It readily
adsorbs compounds with hydroxyl groups and with many of
the more common halogenated hydrocarbons (Thain, 1980;
Altschuller et al., 1962). Organic compounds with a
minimum of three atoms would be trapped on silica gel.
Silica gel adsorbs water more than any other substance;
therefore, under conditions of high humidity, the ef-
ficiency of adsorbing other compounds is much reduced
(Thain, 1980; Buonicore and Theodore, 1975; EPA, 1976).
The addition of a small amount of silica gel in
front of Tenax-GC served to protect the Tenax-GC from the
moisture without altering the efficiency and to trap or-
ganic compounds that were not trapped by Tenax-GC.
To prepare the traps, the tubing was first cleaned
using a soap solution and then distilled water, and was
subsequently rinsed with methanol and oven dried. A
glass wool plug was inserted, and the sorbents were add-
ed, followed by slight tapping an another glass wool plug
to hold the sorbent material.
After trap preparation and before sampling, a clean
trap was analyzed as a blank by Gas Chromatograph-Flame
lonization Detector (GC-FID). Analyses of two traps in-
dicated some quantities of methylene chloride. Investi-
gation revealed that the methylene chloride was a contam-
inant from the laboratory used for oil content analysis.
Subsequently, traps were transferred to and from the
field in an ice chest at 4°C to help avoid contamination
to refrigerate sample.
To start sampling, a quick connect stainless steel
valve was used to connect the trap to the chamber. The
59
-------
use of quick connect valve facilitated sampling and
storage operations. All fittings used were stainless
steel or brass. Two cartridges in series were used
periodically to check for breakthrough. Volatiles were
collected using MDA Accuhaler 808 personal sampling pump.
The length of time of sampling varied depending on
the concentration of the volatiles: after application,
with high concentration of volatiles, 5 minutes; after
tilling, with moderate concentration, 10 minutes; and be-
fore application and tilling, 20 minutes. The collected
samples, which were sealed, labeled and refrigerated in
the field, were analyzed in the laboratory within a week.
Weather permitting, samples were taken before and im-
mediately after application, before and after tilling, as
well as every other week until the next application.
Laboratory Evaluations
Field measurements of volatile hydrocarbons were
complemented by conducting limited exploratory measure-
ments in the laboratory in a temperature and humidity
controlled environmental chamber. Volatilization rates
of the waste were studied at three different tempera-
tures. In addition, for each temperature range, the
application rate was varied. In these tests the soil
moisture content and relative humidity were held con-
stant. Other tests were performed with varying soil
moistures at fixed temperatures and loading rates. The
purpose of this study was to determine the effects of
soil temperature, loading rate, soil moisture content,
and relative humidity on the rate of emission of vola-
tiles. Sludge volatility was kept relatively constant
for all experimental runs by applying one API separator
sludge from the same batch. Prior to each application,
the volatility of the sludge was determined to detect any
60
-------
changes. (Table 5.2 presents the experimental conditions
for the laboratory study.)
For each temperature range four rectangular wooden
boxe>-33 x 31 x 25 cm (13.0 x 12.2 x 9.8 in) filled to a
depth of 20 cm (8 in) with soil from the field research
site were placed in the environmental chamber. The de-
sired air temperature was set and the monitoring chamber
was placed over the soil in one of the boxes.
The appropriate volume of sludge was poured into the
sprayer tank, connected to the monitoring chamber, and
the tank was pressurized to a maximum of 30 psi. When
all of the desired test conditions were stabilized, the
background hydrocarbon concentration was recorded and the
sludge applied evenly over the surface. During the ap-
plication and for one hour afterward, the atmosphere of
head space was continuously monitored using the TLV
Sniffer connected to a chart recorder. After the sludge
was applied and volatiles were monitored, a small garden
hoe was used to completely mix the soil to a depth of 20
cm (8 in).
Each series of experiments was performed over a sev-
en day period. Sampling and monitoring took place before
and during application, immediately after application,
before and immediately after tilling, at two hour in-
tervals throughout the first day of application, and dai-
ly for the next two days. The soil and sludge mixture
was tilled on the third and fifth days after application.
In all, 18 samples were taken with the TLV Sniffer in
each run, and 10 samples were taken for GC analyses, us-
ing adsorbent tubes for each temperature and loading rate
range.
Oxygen Monitoring
Oxygen monitoring was carried out in the zone of in-
61
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'TABLE 5.2. EXPERIMENTAL CONDITIONS FOR LABORATORY
' STUDY
Run.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
Loading Rate
(% oil in
soil-dry wt.)
3
6
10
3
6
10
3
6
10
6
10
6
10
Soil
Temp.
op
35
35
35
60
60
60
85
85
85
60
60
60
60
Soil
Mois. Cont.
(wt %)
12
12
12
12
12
12
12
12
12
23
23
12
12
Relative
Humidity
(%)
52
52
52
52
52
52
52
52
52
52
52
70
70
Air
Flow
Thru
the Box
(1/min)
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
62
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corporation using a Beckman model D2 paramagnetic oxygen
analyzer. This instrument provides a direct readout of
the oxygen concentration as a percentage of the total air
sample.. The monitor utilizes the paramagnetic properties
of oxygen. Air samples drawn into the monitor are
subjected to a magnetic field, which exerts an attractive
force on the sample which is proportional to the amount
of oxygen present in the sample. This attractive force
is translated into a readout of the percentage of oxygen
in the sample.
The sample is drawn into the analyzer via a tube in-
serted to the depth at which the soil atmosphere is to be
monitored. The sample was drawn into the analyzer by
manual operation of a small aspirator bulb.
ANALYTICAL METHODS
Oil Content Analyses
Three different procedures were used in the deter-
mination of oil content. The procedure used with a spe-
cific sample depended on the nature of the sample. The
discussion of procedures is divided into two sections,
sample preparation and analysis.
Sample Preparation
Sample preparation techniques were dependent on the
sample matrix and the moisture content of the sample.
During the research project, an extensive study of sample
preparation techniques for different types of soil sam-
ples were made. Samples can be classified into four dif-
ferent classes:
1. Friable samples (moisture content less than 18
percent for soil used in this study).
2. Wet samples with moisture content approaching
the plastic limit (18 percent).
63
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3. Sludge samples
4. Liquid samples
Class 1
- -"The samples obtained from the field were first mixed
and quartered to obtain approximately 500 gms of soil.
The sample was then blended until it could pass through a
No. 10 sieve. Once the entire sample had been blended
and passed through the No. 10 sieve, the sample was
quartered until the required sample size was obtained.
Class 2--
These samples were difficult to work because of the
inconsistency in the sample and the high moisture con-
tent. The samples were mixed using a mortar mixer, Model
C-100 with intermittent scraping of the soil from the
sides and the blades until a uniform sample consistency
was obtained. The sample was chopped until the particle
sizes were small compared to the overall samples. A flat
2.1 cm (1 in) stainless steel blade spatula was used to
chop the sample. It was then quartered several times un-
til the required sample size was obtained. The sample
was then mixed with a drying agent magnesium sulfate (Mg
SO.) and pulverized in a mortar and pestle.
Classes 3 and 4
Samples were thoroughly mixed and an aliquot of the
sample was taken for analyses.
Analysis
There are three basic methods for oil content analy-
ses as mentioned in the "Standard Methods for the Exam-
ination of Water and Wastewater", 15th edition and the
"Test Methods for Evaluating Solid Waste Physical/
Chemical Methods", July 1982 EPA SW846, 2nd ed. The
three methods are; 1) gravimetric extraction, 2) in-
64
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frared spectrophotometry, and 3) Soxhlet extraction.
The method used in this study was the Soxhlet extraction
method.
.:Two factors which influence the Soxhlet extraction
process .are the solvent used and the method of evapora-
tion of the solvent. The different types of solvent
media used for evaluation of the extractions process
were:
1) 15 percent diethyl ether and 85 percent freon
2) 15 percent diethyl ether and 85 percent
methylene chloride
3) freon
4) methylene chloride
The method of evaporation was varied from that fol-
lowed by Standard Methods wherein the solvent was evap-
orated at 70°C. This procedure resulted in the loss of
volatile compounds in the sample matrix. In order to
avoid loss of volatiles, samples were evaporated on a
steam bath until a volume of approximately 15 ml of solv-
ent was left in the evaporating flask and then transfer-
red to a preweighed aluminum weighing dish. The sample
further was evaporated at room temperature in a hood,
overnight. An inert gas nitrogen (N ) was passed over
the sample to drive off any remaining solvent before
weighing (McGill and Rowell, 1980).
Several methods of extraction were evaluated using
different solvents. The methods were:
(1) Freon Extraction - Method 503-C "Standard Methods
for the Examination of Water and Wastewater".
(2) Soxhlet Extraction with Methylene Chloride - McGill
and Rowell (1980) .
(3) Soxhlet Extract with Freon - modification of method
of McGill and Rowell.
Results of this study, Table 5.3, show the best recovery
65
-------
is the new method using methylene chloride as the solv-
ent. The loading rate for this analysis was 10 percent
oil of dry weight soil.
. TABLE 5.3. COMPARISON OF OIL CONTENT ANALYSIS METHODS
Solvent and Method % of Oil Recovered
of Analysis on a Dry Wt. Soil Basis
1
2
3
Freon, Standard Method
Methylene Chloride,
(McGill and Rowell)
Freon, New Method
(McGill and Rowell)
8.6
9.9
9.4
Fractionation Analysis
This study involves the separation of petroleum res-
idues into four fractions: asphaltenes, saturates, aro-
matics and polar compounds. Polar compounds are also re-
ferred to as resins.
Asphaltenes are defined as pentane insolubles that
can be separated from a solution of oil in n-pentane and
may include insoluble resinous bitumens produced by the
oxidation of oil. Polar compounds are materials retained
on adsorbent clay after percolation of the sample in a
pentane eluent. Aromatics are materials that on percola-
tion, passes through a column of adsorbent clay in a pen-
tane eluent, but adsorbs on silica gel. Saturates are
materials that on percolation in a n-pentane eluent are
not adsorbed" on either the clay or silica gel. The
method used for this separation is the ASTM D2007-73.
Metal Analysis
Heavy metal analyses were carried out on sludges,
site soil, soil/oil matrix, and soil moisture samples.
66
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The sludges and soil samples were analyzed using a diges-
tion procedure obtained from the Environmental Protection
Agency's Robert S. Kerr Environmental Research Laboratory
(RSKERL) in Ada, Oklahoma. In this procedure, between
0.2 and 1 gm of sample was accurately weighed in an
acid-washed beaker, 10 ml of concentrated nitric acid
added to the beaker, and the mixture evaporated just to
dryness. Ten more ml of acid were then added to the
beaker, and the beaker was covered and allowed to reflux
gently for a minimum of 2 hours. When ashing of the sam-
ple was complete, indicated by the absence of -vigorous
reaction, the beaker was cooled, 1 ml of 30 percent
hydrogen peroxide (H202) was added and the digestion
continued. Additional 1 ml portions of H20_ were added
up to a maximum of 10 ml, until digestion was complete.
This stage was denoted by no further changes in the color
of the sample. The cover was then removed from the
beaker, and the sample evaporated until just dry. Three
ml of nitric acid were then added, the beaker heated to
solubilize the residue, and 25 ml of water were added.
The beaker was then covered, and the contents allowed to
digest for 1 hour. The sample was then transferred to a
100 ml volumetric flask, diluted to volume, and analyzed
by Atomic Absorption Spectrophotometry.
Aqueous samples were prepared for analysis using
methods 3010 or 3020 from "Test Methods for Evaluating
Solid Waste Physical/Chemical Methods" July 1982, EPA
SW-846, 2nd ed., published by the Environmental Protec-
tion Agency.
All samples were analyzed on a Instrumentation
Laboratory (IL) Model 551 Atomic Absorption Spectro-
photometer, equipped with a Model 655 furnace and a
model 254 fastact.
67
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Chloride Analysis
, The method used for chloride analysis of soils was
taken,.. from "Methods of Soil Analysis" published by the
American Agronomy Society (Black et al., 1965). Both 1:5
and 1:1 ratios of soil to water were used. The chloride
ion concentration in the soil pore water samples was de-
termined using method 325.3 - titritmetric determination
with mercuric nitrate - taken from the EPA manual "Meth-
ods for Chemical Analysis of Water and Wastes".
pH Determination
The pH determination for soils was done according to
the procedure outlines in Methods of Soil Analysis (Black
et al., 1965) .
The soil sample was diluted 1:1 with water and mixed
for 30 minutes. The mixture was allowed to stand for one
hour to settle, and then the pH was determined using an
Orion Model 401 pH meter with an Orion Model 91-02 elec-
trode .
Nitrate
Soil nitrate determinations were carried out using
the phenoldisulfonic acid method described in Part 2 of
"Methods of Soil Analysis" published by the American
Agronomy Society (Black et al., 1965). This procedure
involves the development of a yellow color with phenol-
disulfonic acid by the nitrate ion in an aqueous extract
of the soil.
Priority Pollutant Analysis
The soil samples were extracted for priority pollu-
tant analysis by using a combination of Methods 3540 and
3530 in the EPA Manual, "Test Methods for Evaluating
Solid Waste Physical/Chemical Methods" July 1982, EPA
68
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SW-846, 2nd ed." In the first part of the procedure, the
solid sample was subjected to Soxhlet extraction using
dichloromethane, as described in Method 3540. The ex-
tract. .from this procedure was concentrated to about 2.5
ml, and 0.5 ml removed for analysis for volatiles. The
remainder was then extracted by Method 3530, yielding
base/neutral and phenolics fractions.
The three fractions obtained in the extraction stage
were then analyzed by a GC/MS system. The system used
was a Hewlett-Packard 5985A Mass Spectrometer, with a HP
5740 Gas Chromatograph and associated data system. Two
different columns were used to analyze the three frac-
tions. The base/neutrals and phenolics were analyzed on
a DB-5, 30 meter, fused silica capillary column, and the
volatiles were determined on a Carbopack C (60-80 mesh)
coated with 0.2 percent carbowax 1500. The conditions
under which the various fractions were run are given in
Table 5.4.
TABLE 5.4. GC CONDITIONS FOR PRIORITY POLLUTANT ANALYSIS
Initial temp.
Initial hold
time
Ramp rate 1
(time in min.)
Ramp rate 2
Final temp.
Detector temp.
Injection temp.
Run time
Volatiles
60°C
3 min.
8° /min.
-
160°C
200°C
175°C
25 min.
Base-Neutrals
50°C
1 min.
30°/min. (2)
8° /min.
300°C
200°C
250°C
40 min.
Phenolics
60°C
1 min.
30°/min. (2)
8° /min.
270°C
200°C
200°C
20 min.
Carrier gas - Helium
Flow rate - 14 ml/min. for capillary column
25 ml/min. packed column
69
-------
Standards were run at the start of each day's analy-
sis, and identified from the mass spectrum of each peak
obtained in the chromatogram. The unknown samples were
run :.and the resulting data stored on a computer disk.
A JT
Once all the samples were run, a standard file library of
all the standards was created using a computer program
written for identification and quantification called the
IQ program. Each fraction - volatiles, base-neutrals and
phenolics - had its own file. A data file was set up for
the sample fractions, and matched against the files for
the standards. The resulting printout was then analyzed
for matches between the standards and unknown samples,
and the concentrations of the compounds identified in the
samples were calculated using response factors for the
standards.
Air (Volatile Organics)-
The collected samples were analyzed in the laborato-
ry within a week by Hewlett-Packard (HP) Model 7675 purge
and trap system and HP Model 5880A Gas Chromatograph (GC)
equipped with Flame lonization Detector (FID). A 0.32 cm
(0.13 in) stainless steel column, packed with carbopack
B/l percent SP-1000 was used to separate the hydrocarbon
compounds thermally desorbed from the sampling cartridge.
Recovery of trapped vapors was accomplished using thermal
desorption which allowed for direct introduction of the
total sample into the GC column. Limited Gas Chromato-
graphy-Mass Spectrometry (GC-MS) analysis was also per-
formed in the EPA's Robert S. Kerr Environmental Research
Laboratory (RSKERL) in Ada, Oklahoma for quality control.
The identity of volatile compounds was based on re-
tention times of standard compounds and confirmed from
subsequent GC analyses. Relative concentrations of com-
pounds were determined using the Internal Standard (ISTD)
70
-------
Calibration Method. Absolute quantities could not be
given, since it was not known for all samples whether
breakthrough has occurred from the sorbent trap. First,
1,4-dichlorobutane was used as an internal standard.
However, with the last batch of sludge one compound co-
eluted with 1,4-dichlorobutane, and they could not be
separated by changing temperature programming nor even by
using a capillary column. Therefore, after trying many
compounds, methylene chloride was chosen to be used as an
internal standard.
Since petroleum sludge contains a complex mixture of
organic compounds, chromatographic separation of such
compounds was a difficult task. Three different GC col-
umns, including 60/80 carbopack C/.2 percent carbowax
1500, 10 percent SP-2100 on 100/120 suplecoport. and 60/80
carbopack B/l percent SP-1000, were examined at different
conditions. It was found that 60/80 carbopack B/l per-
cent SP-1000 gave the best resolution. Nevertheless,
peaks frequently overlapped, and it was difficult to
identify and quantify all the unknown compounds. Thus,
it was essential to reduce the number of organic com-
pounds to be quantified. Of the volatile hydrocarbons
identified, only fifteen were quantified. Table 5.5 pre-
sents these target compounds along with their retention
times.
A calibration mixture of the fifteen compounds which
were quantified (Table 5.5) was prepared every week. The
purge and trap and GC were tested every day before the
analysis of samples. The clean trap was then easily
changed to the sample trap in the purge and trap system.
A leak test was performed to confirm that all fittings
were tight. Internal standard was first purged into the
sample trap in a known concentrations. Nitrogen gas was
used as a purge gas. Purge flow was maintained at 50
71
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TABLE 5.5.POLLUTANTS IDENTIFIED AND QUANTIFIED IN
AIR SAMPLES ALONG WITH THEIR RETENTION
Chroma tographic
Pe'afc "Number
*1
2
*3
4
*5-
6
7
3
9
10
*11
12
13
14
15
16
17
18
19
*20
*21
*22
*23
*24
*25
Compound
Propanol
Methylene Chloride (IS)
2-Propanone
Cyclopentane
2-Butanone
Pentane
Cyclohexane
Methylcyclopentane
Benzene
Methylcyclohexane
2 , 4-Dimethylpentane
Hexane
3-Methylhexane
1 , 4-Dichlorobutane (IS)
2,3, 4-Trimethy Ipentane
2 , 5-Dimethy Ihexane
3-Methylheptane
2,2, 5-Trime thy Ihexane
Retention
Time (min)
8.71
9.30
9.56
13.47
18.05
19.58
21.06
22.36
26.84
29.84
31.46
32.95
35.58
37.23
38.995
42.76
44.65
46.67
1 ,4-Dimethylbenzene 57.12
2-Pentanone
Cyclohexanol
Ethylcyclopentane
2-Methyl-l-Pentanol
1 , 1-Dimethylcyclopentane
Cis-1, 2-Dimethylcyclopentane
* These hydrocarbons were only identified, not quantified
72
-------
ml/min for 10 minutes. Trapped volatiles were then
thermally desorbed at 250°C and backflushed to the GC
column. Optimum results were achieved by temperature
programming from 45°C to 200°C at 4°C/min with initial
and final isothermal periods of 2 and 20 minutes, respec-
tively. Carrier gas (nitrogen), hydrogen and air flow
rates were 30, 30, 450 ml/min, respectively. Flow rates
were checked by a bubble tube flow meter every day before
analysis began. The injector port and detector tempera-
tures were 250°C. Analysis time was approximately 60
minutes. Table 5.6 summarizes the GC conditions for the
analysis of hydrocarbon components. At the end of each
analysis, the column was cooled to 45°C for the next
analysis.
A small amount of carry-over (less than five per-
. cent) of the heavier compounds was observed from the con-
centrator when a blank was run immediately after the con-
centrated sample. Thus, in order to have a clean trap
for the next sampling, a blank was run on the same trap
immediately after each analysis.
Sludge Volatility
A simple laboratory test was devised to measure the
extent of hydrocarbon emissions to be expected from the
land treatment of a given sludge. The basic idea of this
test was to purge an inert gas (hydrocarbon-free air)
through a small sludge sample and to sweep all volatile
hydrocarbons out of the sample.
For the volatility test, a 25 ml impinger, com-
pressed air and TLV Sniffer were used. Figure 5.6 de-
picts a diagram of volatility test set up.
The experimental procedure involved the following
steps:
1. The empty impinger tube was first weighed.
2. The tube was filled with 15 ml of sludge sample
73
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TABLE 5.6. PURGE & TRAP AND CHROMATOGRAPHIC CONDITIONS
FOR THE ANALYSIS OF HYDROCARBON COMPONENTS
1. Purge & Trap Conditions:
Prepurge Time
Nitrogen Purge Flow
Purge Time
Desorb Temperature
Desorb Time
Auxiliarly Temperature
Vent Time
2. GC Conditions:
Nitrogen Flow (carrier gas)
Air Flow
Hydrogen Flow
Detector Temperature
Injector Port Temperature
Oven Temperature
Chart Speed
Attenuation
3 minutes
50 ml/min
10 minutes
250°C
10 minutes
200°C
10 minutes
30 ml/min
450 ml/min
30 ml/min
250°C
250°C
45°C Initial, to
200°C at 4°C/min
.5 in/min
8
74
-------
How Meter
Regulator
,TT
Hydrocarbon and
Moisture Trap
Compressed Air
Figure 5.6. Stripping test setup.
75
-------
and weighed.
3. The stripping apparatus was set up.
.4. The flow rate of air (purge gas) through the
. o... sludge sample was adjusted to 2 1/min in all
stripping runs.
5. The hydrocarbon concentration in the stripping
air was monitored with TLV Sniffer at 5 minute
intervals for two hours, a constant time in all
stripping tests.
6. The compressed air and TLV Sniffer were removed
or disconnected from the impinger tube at 10-
minute intervals and the impinger tube contain-
ing sludge was weighed.
7. The percentage volatile loss was calculated
from the difference in sludge weight.
8. The data collected allowed for evaluation of
the weight loss rate and a determination of the
relationship between concentration (reading
taken with TLV Sniffer) and weight volatilized.
Quality Assurance/Quality Control
A QA/QC program was implemented at the beginning of
the project. This program had two main parts. Part 1
involved sample collection, transportation and storage,
and Part 2 involved the determination of blanks, repli-
cates and spikes.
Each sample collected was assigned an identifying
code, which contained information on the plot no., date
and type of sample collected. Samples were placed in a
cooler immediately upon collection until they could be
transported to the laboratory and refrigerated. The
aqueous samples were stored in a refrigerator, at 4°C,
until they were analyzed. Soil samples were collected in
plastic bags and aqueous samples in borosilicate glass
76
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bottles with Teflon-faced screw caps. A log book of all
site visits and samples collected was maintained. Aque-
ous s'amples to be analyzed for metals were adjusted to pH
less'.; than 2 with concentrated nitric acid as soon as they
arrived at the laboratory. COD and pH analyses were per-
formed on the samples within 24 hours of collection. All
samples for priority pollutant analysis were extracted
within one week of collection, and analyzed within one
month of extraction.
Glassware used for priority pollutant analysis was
solvent washed, detergent washed, rinsed with tap water,
distilled water and oven-dried. The K-D (Kuderna-Danish
apparatus) flasks and concentrators were also cleaned
with chromic acid prior to each set of extractions.
After each batch of samples from one site was run, the
glassware was heated to 400°C in a furnace after the
cleaning sequence described above.
Glassware for metal analyses was washed with deter-
gent, and then acid-rinsed with nitric and hydrochloric
acids. After a final rinse with distilled water, the
glassware was oven-dried. Glassware used for other anal-
yses were cleaned using standard laboratory cleaning pro-
cedures .
The quality control procedures used in the deter-
mination of priority pollutants centered mainly on the
determination of blanks and the use of duplicate deter-
minations. Pesticide grade solvents were used in all ex-
tractions. Spikes were also determined on the aqueous
samples. No studies were done on recoveries from the
different soil matrices, because of time and money re-
strictions.
The GC/MS system was tuned on a daily basis with
perfluorotributylamine (PFTBA). Decafluorotriphenylphos-
phine (DFTPP) Standards were run to check the relative
77
-------
ion abundance. The mass spectrometer source was heated
to a temperature of 274°C periodically to remove contami-
nants.
".Duplicates, spikes and blanks were also run on the
samples analyzed for metals.
Oil Content
Background soil samples were obtained from the field
to represent the matrix of the soils to which the oily
residues were applied. The background soil samples were
spiked with a known amount of oily residue. The samples
were extracted using the revised Soxhlet extraction pro-
cedure. The results are tabulated in Table 5.7. The
mean recovery was found to be 96.2 percent.
TABLE 5.7. OIL RECOVERY FROM SPIKED SAMPLES
No. % Oil Recovered
1 9.37
2 9.78
3 9.69
Mean 9.62
% Oil Applied
10.0
10.0
10.0
10.0
Fractionation Analysis
Reference standards for quality control were ob-
tained from EPA through their quality assurance program.
The reference standard used was the Kuwait Crude Oil.
Two analysts performed the extractions. The results of
the recoveries by the two analyses are presented in
Tables 5.8 and 5.9. The method of analysis was the ASTM
- D2007.
78
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TABLE 5.8.
RESULTS OF ANALYSIS OF KUWAIT CRUDE OIL
FOR QUALITY CONTROL - ANALYST 1
No. -
1
2
3
4
5
6
7
Mean
EPA Ref,
Value
Saturates
39.10
30.20
35.10
36.10
35.60
36.30
35.80
35.46
32.30
Aromatics
40.0
52.0
47.4
46.0
45.5
44.8
45.6
45.9
47.6
Polar
Compounds
16.80
13.40
14.50
13.90
14.60
14.50
14.30
14.57
16.90
Asphaltenes
4.1
4.4
4.0
4.0
4.3
4.4
4.3
4.21
3.20
TABLE 5.9.
RESULTS OF ANALYSIS OF KUWAIT CRUDE OIL
FOR QUALITY CONTROL - ANALYST 2
No.
1
2
3
4
5
6
7
8
9
10
Mean
EPA Ref,
Value
Saturates
33.00
32.80
36.00
35.60
32.30
33.60
34.20
33.80
33.50
32.00
33.68
32.20
Aromatics
48.4
47.7
44.9
44.8
47.7
47.0
46.4
47.0
46.7
48.4
46.9
47.6
Polar
Compounds
14.30
15.30
14.90
15.20
15.70
15.20
15.20
14.90
15.70
15.10
15.15
16.90
Asphaltenes
4.3
4.2
4.2
4.4
4.3
4.2
4.2
4.3
4.1
4.5
4.27
3.2
pH - standardization of the meter before use and the
determination of duplicates on soil samples. For aqueous
samples only one determination per sample was possible.
Nitrate and phosphate - a standard was run with each
set of samples to check the calibration curve, and one
79
-------
duplicate determination was carried out for each set of
samples.
.'COD - quality control was by means of blanks and
duplicates.
Volatile Organics
The quality assurance and quality control program
for the volatile emission study was as follows:
1. The TLV Sniffer was calibrated every two
months. The calibration was check with known
concentrations of hexane prior to and after
each sampling.
2. The sampling pump was calibrated before and af-
ter sampling, using a bubble flow meter.
3. Chain of custody forms were maintained for each
sample.
4. Upon return from a sampling trip, each sample
code and the results obtained from TLV Sniffer
and other monitoring equipment were entered in
a sample log book. This log was updated as
samples proceeded through work up and analysis.
5. Vials for standards, glassware etc., were
cleaned with soap and water, rinsed with de-
mineralized water and methanol, and heated to
450-500°C to insure the removal of all traces
of organic compounds.
6. After the preparation of a set of sampling car-
tridges, one cartridge was checked for back-
ground prior to the cartridge's commitment to
field sampling.
7. All sampling cartridges were transferred to and
from the field in an ice chest at a temperature
of 4-10°C.
8. If two cartridges were used in series to check
for breakthrough, they were separated and
80
-------
sealed individually immediately after sampling
to avoid errors arising from diffusion which
might have occurred later.
9. The collected samples were analyzed within a
week.
10. To insure the accuracy and precision of the da-
ta acquired, instrument and chromatographic
performance were monitored as follows:
(a) The linearity of the gas chromatograph was
verified once a week. Three different
concentrations of working calibration
standards were used to obtain instrument
response with thirteen compounds. When
sample concentration versus instrument re-
sponse was plotted, the result fell along
a straight line.
(b) A strict step-sequence of analysis was
followed. At -the start of each working
day, the analysis cycle began with the
blank (using organic-free water), the
multi-component working standard and three
samples. Each sample was followed by a
blank. This way, the purge and trap and
GC column performances were monitored ev-
ery day. Running the blank also indicated
that the syringe, needle and all lines
from the purge and trap through the injec-
tion port and the FID were free of contam-
inants.
11. Each sample run by GC was logged into a note-
book, detailing analysis conditions, compounds
found and where the data were archived.
12. Periodically, duplicate samples were analyzed
by GC-MS at the RSKERL EPA Laboratory in Ada,
Oklahoma.
31
-------
SECTION 6
RESULTS AND DISCUSSION
The primary emphasis of this project was to deter-
mine the rate of loss of oil from plots with a range of
oil concentrations due to varying loading rates and fre-
quencies. Secondary objectives were to determine losses
due to migration and emissions to the atmosphere and to
determine the presence and fate of certain priority pol-
lutants. This section of the report presents the . data
collected during the study period and an interpretation
of the data in terms of the stated research objectives.
These objectives were discussed in Section 1. Reference
should be made to Section 5 for a discussion of relevant
analytical and experimental methods.
FATE OF OIL IN THE SOIL ENVIRONMENT
One of the stated research objectives was to estab-
lish loading rate and loading frequency guidelines.
Thus, the objectives of this portion of the research were
not only to establish the fate of oil in the soil en-
vironment, but to identify the optimum process condi-
tions .
The mere disappearance of oil from the surface soil
environment without regard to its ultimate fate is not
the only criterion of optimization. It is important to
identify those processes contributing to oil disappear-
ance which are to be maximized and those which are to be
minimized. Clearly, run-off, deep percolation and
82
-------
volatilization should be minimized, while biological deg-
radation and photodegradation should be maximized. Run-
on ijs controlled by placing an earthen berm around the
active site. Deep percolation is minimized by selecting
a site underlain with an impervious clay layer and by
maintaining aerobic conditions in the zone of incorpo-
ration. Volatilization can be limited by subsurface in-
jection if air pollution standards are violated by sur-
face spreading, and by tilling under optimum environ-
mental conditions.
Biodegradation of oil occurs principally in the zone
of incorporation, with much less biological activity oc-
curring at lower depths. Thus, the zone of incorporation
may be considered a bioreactor in which conversion of
substrate to various end-products occurs. This biore-
actor operates in a quasi-completely mixed mode. Peri-
odic measurements of substrate concentration within the
bioreactor facilitate the evaluation of the rate of sub-
strate disappearance from the zone of incorporation.
Combined with information on other mechanisms of disap-
pearance such as percolation, runoff, and volatilization,
zone of incorporation oil content measurements allow
evaluation of the biokinetic rates which are needed to
optimize the process.
A fundamental measure of process kinetics is the ki-
netic order and rate with which reactions take place. If
a reaction such as oil disappearance proceeds at a rate
independent of the oil concentration or of any other re-
actant, then the reaction is said to be zero-order.
Thus, if C, represents the concentration of oil at any
time t; the disappearance of oil is described by the
kinetic equation:
dc - TC
dt ~ ~K
83
-------
where K is the zero-order reaction rate constant. A plot
of oil content with time for a zero-order rate of disap-
pearance is linear, with a slope equal to -K.
.: In contrast, first-order reactions proceed at a rate
which is directly proportional to the concentration of
the reactant. The following equation summarizes first-
order reaction kinetics:
d£ _
dt ~ KC
integration of this equation yields:
In ^ = Kt
Ct
thus, a plot of In C versus time yields a linear plot for
a first-order reaction.
Higher order reactions are possible and, in fact,
highly likely considering the complex nature of the
sludge and the variety of microorganisms which utilize
the various fractions of organics. However, models based
on higher order kinetics have not increased the precision
in predicting rates of removal or removal efficiencies in
other waste treatment studies. For the purposes of this
study, pseudo first-order kinetics is sufficient to meet
the objectives of the project.
Evaluation of Oil Content Data
Data from oil content analyses developed using meth-
ods previously described were recorded in laboratory
notebooks and later entered into computer files for docu-
mentation and data manipulation. Information in each
file consisted of sample date, plot sampled, values of
oil content for each of the three composite samples from
each plot, name of analyst, date of analysis, and refer-
84
-------
ence to the laboratory notebook entry.
Raw oil content data from the zone of incorporation
is sorted by plot number and ascending date and tabulated
in Table A.2, Appendix A. In order to obtain a time se-
ries oil content 'history1 for each plot, the analysis
and loading data were merged to form the data sets pre-
sented in Table A.3, Appendix A.
These time series oil content histories include cal-
culated values based on the amount of oil applied plus
oil existing at a given time. Samples were generally
collected immediately before application and the oil con-
tent determined. The oil content of this sample plus the
oil applied equals the calculated after application oil
content value. Similarly, if a plot was sampled follow-
ing an oil application, the quantity of oil applied was
subtracted to give a calculated before application value.
In several cases a plot was sampled both before and after
application to verify the amounts of oil applied.
Since the reliability of the analyses as estimates
of the true mean oil content of a given plot is of prima-
ry importance, a screening methodology was used to iden-
tify any outlying values.
As discussed above in reference to the effect of
sample preparation methodology on data variability, the
coefficient of variation was computed for each set of
analyses on a given plot and date. In the initial
screening process, raw data for which the internal co-
efficient of variation was greater than 0.15 were flagged
as possibly including an outlier. After loading data and
analysis data were merged, the oil content data were
graphed as a function of time for each test plot. These
graphs may be found in Figures A.I through A.32.
Several items are noteworthy with respect to Figures
A.I through A.32. Since oil content data prior to Sep-
85
-------
tember 9, 1982 was taken before the oil analysis and
sampling methods were finalized, the data was not reli-
able- Therefore, it was not possible to construct the
portion of the load loss curves covering the first proj-
f r
ect year. Although data points are shown for all oil
content data found in Table A.3, lines have only been
drawn through those points which were used in data analy-
ses as discussed below. Discontinuities are due to in-
sufficient data. The dormancy period, period of low
activity, which occurred during winter (elapsed days
486-598) was indicated with a solid line on those plots
for which data adequate to describe this period. A
dashed line was used on those plots which were only sam-
pled at a time two or three months after the end of the
dormancy period.
Based on a preliminary knowledge of the processes
occurring, several criteria were developed with which
anomalous values of oil content were identified. The
criteria were based on apparent impossibilities such as
the following:
1. Oil content should not increase without the ad-
dition of a sludge.
2. Though it was reasonable to assume that the
samples taken after application could have a
lower measured oil content than the calculated
value (based on before application samples plus
oil applied), the calculated oil content of
value could not be lower than the measured val-
ue.
3. Degradation of the oil was assumed to follow
zero or first-order kinetics, thus, if the form
of the loss curve did not reflect this charac-
teristic, the data was reviewed to determine
why a difference existed.
86
-------
If, when reviewing the data, such apparent impos-
sibilities were found to exist, reference was made to the
values of internal coefficient of the variation of the
offending data. If a high Coefficient of Variation
(C.V.) was found, reference was then made to the raw data
to identify an outlier. If no outlier was present, then
the anomaly was allowed to remain. If one of the raw
data points was much different from the other values, a
check was performed to see if any improvement in the C.V.
could be made by dropping the outlier in the computation
of the mean oil content. If dropping the outlier
decreased the C.V., the outlier was dropped.
-The time series oil content histories, corrected for
outliers, is thus the basis for evaluation of the biode-
gradation process. The following discussion outlines the
statistical techniques employed to describe the data and
to compare different sludge loading treatments in terms
of the objectives of process optimization.
Oil Content Data Evaluation
There were many field conditions encountered by the
research team which adversely impacted the project. Dur-
ing much of the study period, wet weather limited the ac-
tivities which could be performed at the research site.
In particular, application and sampling frequencies were
dictated by the weather. Differing antecedent soil con-
ditions prevented full applications to several plots, in-
cluding replicates of some plots which were fully loaded.
Thus, there were many factors which precluded the use of
the originally proposed factorial-type experimental de-
sign. Among these were: 1) the variation from nominal
oil loadings received by the plots; 2) the irregular
frequency with which the applications could be made; 3)
the inability to apply the required amount of oily sludge
87
-------
to the plots receiving high rate - low frequency treat-
ments; and 4) the inability to till some of the plots
immediately following application of heavy oil loads,
thus'.>,,introducing another process variable into the ex-
perimental design.
Only three sets of original plots received replicate
treatment. The lack of replication had the combined ef-
fect of reducing the statistical significance of the ex-
perimental data, as well as vastly increasing the com-
plexity of the data evaluation.
Despite the problems associated with a change in the
statistical plan of analysis of the oil content data,
several data analysis methods were identified which could
be applied to the available data. These investigations
were aimed at evaluation and comparison of loss rates
based on loading rates and frequencies.
The following analyses were performed using the oil
content data.
1. Total oil losses during the first year of the
project were developed from the loading data
and the oil content analysis performed in Sep-
tember 1982.
2. Total oil losses during the second year of the
study were developed and compared with the
first year's losses.
3. Total oil losses throughout the entire project
until June 1983 were determined.
4. Loss rates and reaction order were investigated
and rate coefficients were developed for sever-
al plots using oil content data collected in
the Fall of 1982 and the following year.
5. Evaluation was made of the data comprising the
cyclic loading/loss portions of the time series
curves of several plots. This evaluation deals
88
-------
primarily with the higher application frequency
plots for which data covering more cycles ex-
ist. Though kinetic order cannot be determined
;] from this data, both zero order and first-order
rate coefficients were calculated.
6. Data on volatile emissions of certain plots was
incorporated with the zone of incorporation
loss data during the Fall of 1982, thus, sep-
arating this loss mechanism in the analysis.
First order loss rates were recalculated based
on this data.
7. The winter dormancy period was evaluated for
several plots.
Based on availability of sufficient reliable data the
plots were allocated for the particular investigation as
shown in Table 6.1.
Total Oil Losses During First Study Year
The purpose of this analysis was to determine total
oil losses and relate these losses to the factors which
control them. Since the sludge loading data for each ap-
plication is known, only one analysis at the end of the
first year is required to compute the first year total
losses for a particular plot.
For the purposes of discussion, the units of oil
content and loading rate have been calculated on a per-
cent oil based on the dry weight of the soil (% dwb) ,
using constant plot dimensions of 2.75 m (9 ft) x 6.10 m
(20 ft) x 0.30 m (1 ft) and a dry soil specific weight of
1282 kg/m3 (80 lb/ft3).
The total percent (dwb) of oil applied to each plot
was calculated and the percent of oil remaining in the
soil after 385 days subtracted to give the percent of oil
lost. The gross loss was also computed in terms of per-
89
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TABLE 6.1. PLOT ALLOCATION TO VARIOUS DATA EVALUATIONS
Total Loss
Los-ses Rates
1981-
1982
8
10
15
16
17
21
22
23
24
28
29
30
31
35
Loss
Rates
1982-
1983
4
5
9
10
14
15
20
24
25
29
30
34
35
Cyclic
Loading
Period
1
2
4
5
6
7
-
9
11
13
14
18
20
25
26
32
Dormancy
Period
4
5
9
10
14
15
20
24
25
29
30
34
35
Losses
Other
Than
Emissions
1
4
5
6
7
90
-------
cent of the total first year loading. These values have
been tabulated in Table 6.2. From this data it is evi-
dent.' that total losses increased with an increase in
loading rates. Total loss (% dwb) as a function of total
r »
loading (% dwb) for the first study year indicated a good
linear trend between these variables, correlation coeffi-
cient equal to 0.91. Regressing percent of total loading
lost as a function of total loading resulted in a lower
correlation coefficient.
Since the above analysis does not take into account
the time the plots were loaded, a method was devised to
relate total losses to a time-loading moment. Each in-
dividual loading was multiplied by the time interval from
the loading date to the date of analysis (day 385) and
the resulting products summed to yield a value which in-
corporates elapsed time until analysis with the anteced-
ent loading. Total losses as a function of the total
time-loading moment are shown in Figure 6.1. Total
losses as a function of time-loading moments for all
plots gave a correlation coefficient of 0.96 which
indicates that the combined effect of total loading and
elapsed time is greater than the effect of total loading
alone. It is also evident that the total losses are
greater for plots which received few heavy applications
early in the first project year, than for plots which
received more frequent low applications over the entire
year.
Total Losses During Second Study Year
Total oil losses were computed for the second study
year as presented in Table 6.3. A trend similar to that
shown during the first study year is evident, with total
losses roughly proportional to the sum of antecedent oil
from the first year plus the applied oil during the sec-
91
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TABLE 6.2. TOTAL LOSSES DURING FIRST STUDY YEAR
Plot.
1
2
4
5
6
7
8
9
10
11
13
14
15
16 .
17
18
20
21
22
23
24
25
26
28
29
30
31
32
34
35
36
38
First
- Year
Loading
(% dwb)
9.61
5.81
2.01
6.62
15.04
5.08
19.03
2.62
7.86
3.93
5.36
2.01
7.86
6.90
6.90
1.34
8.54
14.90
16.68
17.44
4.03 .
1.64
7.06
12.75
11.00
10.75
6.90
2.62
5.37
12.96
12.62
4.03
Oil
Content
Analysis
(% dwb)
7.79
3.99
1.07
3.89
9.49
3.08
8.18
1.59
3.63
2.59
3.58
1.61
4.04
4.06
2.75
1.10
5.11
6.34
8.66
9.72
2.73
1.50
4.20
8.46
5.79
4.49
2.00
2.17
3.10
5.37
8.42
3.50
Total % of
Oil First
Loss Year
Loading
(% dwb) Lost (%)
1.82
1.82
0.94
2.73
5.55
2.00
10.85
1.03
4.23
1.34
1.78
0.40
3.82
2.84
4.15
0.24
3.43
8.56
8.02
7.72
1.30
0.14
2.86
4.29
5.21
8.16
4.90
0.45
2.27
7.59
4.20
0.53
19
31
47
41
37
39
57
39
54
34
33
20
49
41
60
18
40
57
48
44
32
9
41
34
47
58
71
17
42
55
33
13
Time-
Loading
Moment
(%dwb*day)
1278
941
299
960
2014
691
5576
445
1352
538
822
231
1360
2201
2139
206
1196
4619
4687
3087
544
261
967
1733
1782
3069
2132
453
843
4070
2600
725
92
-------
11-
10-
9-
T 8-
R
L
0
I
L
7-
L 6-
0
S
S
( 5-
P
E
R
C
E "4-
N
T
D
H 3-
B
)
2-
1-
0-
+
f
500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500
TIMExLOflDING MOMENT (PERCENT OWB«DflT)
Figure 6.1. Total loss (% dwb) vs time loading moment,
first year data.
93
-------
TABLE 6.3. TOTAL LOSSES DURING SECOND STUDY YEAR
Plot,
1
2
4
5
6
7
8
9
10
11
13
14
15
16
17
18
20
21
22
23
24 .
25
26
28
29
30
31
32
34
35
36
38
Initial
Elapsed
Time,
(day)
384
384
384
384
409
384
355
397
385
384
384
384
385
385
385
397
384
385
385
385
385
385
384
385
385
385
385
384
384
385
385
385
Initial
Oil
Content
(%dwb)
7.79
3.99
1.08
3.89
9.49
3.08
8.18
1.59
3.64
2.59
3.58
1.61
4.04
4.07
2.75
1.10
5.11
6.34
8.66
9.72
2.73
1.50
4.21
8.46
5.79
4.50
2.00
2.17
3.10
5.37
8.42
3.50
Total
2nd
Year
Loading
(%dwb)
10.43
4.97
2.12
8.26
5.00
3.45
7.74
2.28
6.90
4.60
3.84
2.28
6.90
3.45
1.72
1.45
5.76
7.47
5.75
.4.23
3.45
0.58
5.00
11.50
11.50
3.45
1.72
2.18
2.88
5.75
3.97
3.45
Day 657
Final
Oil
Content
(%dwb)
10.82
6.76
1.62
7.00
8.16
4.94
9.68
3.05
6.85
4.57
4.51
2.12
7.88
5.43
7.84
1.39
5.46
7.12
8.57
6.40
4.13
1.33
5.06
11.32
9.98
2.51
1.87
2.27
4.19
5.24
7.32
4.11
Total
Second
Year
Loss
(%dwb)
7.4
2.2
1.58
5.15
6.33
1.59
6.24
0.82
3.69
2.62
2.91
1.77
3.06
2.09
1.63
1.16
5.41
6.69
5.84
7.55
2.05
0.75
4.15
8.64
7.31
5.44
1.85
2.18
1.79
5.88
5.07
2.84
94
-------
ond year.
Second year total losses as a function of second
year, oil loadings yields a correlation coefficient of
0.81;. Total losses as a function of the sum of the first
f =
year antecedent oil content plus second year oil loading
yields a correlation coefficient of 0.94, indicating that
total oil loss is a function of the total oil content not
just that applied during the second year.
Total Losses Over Two Year Period
Total oil losses over the two year study period were
evaluated in much the same way as the first year's data
(Table 6.4). Oil content values determined for samples
taken June 9, 1983 were subtracted from the total percent
applied to each plot to give the percent lost over the
approximate two year study period (657 days). Percent of
the total oil loading lost was then computed. The aver-
age percent of oil lost per day was computed by dividing
the percent lost by the number of days elapsed from the
first application date until the June 9, 1983 analysis.
Analysis of this data revealed a strong linear rela-
tionship between average percent of oil lost per day and
total percent applied over the study period. A plot of
this data is presented in Figure 6.2. The correlation
coefficient associated with a linear regression of per-
cent dwb of oil lost per day on total oil loading was
0.95.
Time-loading moments, about the June 9, 1983, anal-
ysis date were computed for each plot as discussed for
the first years loadings. Percent lost as a function of
time-loading moment yielded an extremely high correlation
coefficient of 0.99.
The total loss data for the first year, the second
year, and for the entire study period indicates that oil
95
-------
TABLE 6.4. TOTAL LOSSES DURING TWO YEAR STUDY PERIOD
Plot,
f tr
1
2
4
5
6
7
8
9
10
11
13
14
15
16
17
18
20
21
22
23
24
25
26
28
29
30
31
32
34
35
36
38
Time-
Loading
Moment
(%dwb/day)
6358
3581
1326
4645
6858
2884
12306
1606
4954
2691
3127
1364
4978
4784
4363
905
4871
10186
10395
8552
2544
856
4139
8335
7209
5921
4363
1656
2951
7819
6709
2544
Percent
dwb Lost
(%dwb)
9.22
4.02
2.52
7.89
11.88
3.59
6.15
2.44
7.91
3.96
4.68
1.62
6.88
4.92
5.79
1.39
8.84
15.69
13.86
14.24
3.34
0.88
6.98
13.40
12.51
11.68
6.75
2.64
4.05
13.46
5.23
3.37
Percent of
Total
Lost
(%)
46.0
37.3
60.8
53.0
59.3
42.1
63.5
44.5
53.6
46.4
50.9
43.3
46.6
47.5
67.1
49.9
46.6
68.8
61.8
65.7
44.7
39.8
58.0
54.2
55.6
82.3
78.3
53.7
49.2
72.9
41.7
45.1
Average
Percent dwb
Lost per
Day
(% dwb/day)
0.014
0.007
0.004
0.012
0.018
0.005
0.026
0.004
0.012
0.006
0.007
0.002
0.011
0.008
0.010
0.002
0.011
0.024
0.021
0.023
0.005
0.001
0.011
0.020
0.019
0.018
0.010
0.004
0.006
0.020
0.008
0.005
96
-------
O.U275-
0.02SO-
0.0225-
V O.J200-
r
ft
3
C
E 0.0175-1
p
C
N
~ 0.0150-
0
8
q
5
7
P
E
ft
0.0125-
0.0100-
0 0.0075-
V
O.UOSO-
O.U02S-
*
(
( -f
i- -I- 4-
4- -i-
U.OOOO-
0 2 k 6 8 10 12 l>i 16 16 20 22 24 26
TOTflL CUMUL3T3VE PERCENT 0*8 flPPLliO
Figure 6.2. Percent (dwb) lost per day vs total
percent (dwb) applied to date.
97
-------
losses increase in proportion to the increase in total
oil loadings. The time elapsed since application is also
an important factor especially during the first few years
until..equilibrium is reached.
An average of 54 percent of the total oil applied
disappeared during the overall study period of 657 days
with a range from 37.3 to 82.3 percent. This contrasts
the data presented in the first year for which the
average percent of applied oil lost was equal to 39.6
percent with a range from 9 to 71 percent.
Kinetic Rate Evaluation for First Year
Several plots were selected for an investigation of
kinetic order and loss rates at the end of the first
study year. The criteria for selection was that there
were at least three reliable oil content values available
between the last application of the first year to the
first oil application in the second year.
Data of the type required for this investigation was
available for fourteen plots. For each of the plots, the
mean oil content values as a function of elapsed time
from the first application date yielded zero order
slopes. Correlation coefficients were used to test good-
ness of fit. First order rates were obtained by evalua-
tion of the natural logarithm of mean oil content as a
function of elapsed time. The corresponding correlation
coefficient obtained gives an indication of the goodness
of fit.
The results of the regression analyses are given in
Table 6.5. As can be seen from this data, plots 16, 17,
29, and 31 all showed fairly good linearity as both zero-
order and first-order functions, with the first order
kinetics appearing slightly more highly correlated.
Though correlation coefficients are not as strong for the
98
-------
TABLE 6.5. KINETIC ORDER AND LOSS RATES
FOR FIRST STUDY YEAR
vo
10
Plot
8
10
15
16
17
21
Elapsed
Time
(days)
385
401
453
385
401
444
385
401
444
385
401
. 453
385
401
453
385
401
445
453
Mean Oil
Content
(%dwb)
8.18
7.30
6.77
3.64
3.32
3.31
4.04
4.08
3.14
4.07
4.00
3.33
2.75
2.42
1.83
6.34
5.13
4.80
.4.62
In of
Mean Oil
Content
2.10
1.99
1.91
1.29
1.20
1.20
1 .40
1.41
1.14
1.40
1.39
1.20
1.01
0.88'
0.604
1.85
1.64
1.57
1 .63
Zero Order First Order
Rate R^ Rate R2
0.018 0.82 0.0025 0.86
0.0045 0.53 0.0013 0.53
0.0166 0.91 0.0046 0.91
0.011 0.98 0.0031 0.98
0.013 0.98 0.0058 0.99
0.021 0.78 0.0038 0.80
(continued)
-------
TABLE 6.5. (continued)
o
o
Plot
31
35
Elapsed
Time
(days)
385
401
453
385
401
444
453
486
Mean Oil
Content
(%dwb)
2.00
1.91
1.66
5.37
4.44
3.87
3.66
2.48
In of
Mean Oil
Content
0.693
0.647
0.507
1.68
1.49
1.35
1.30
0.91
Zero Order First Order
Rate R Rate R2
0.0050 0.99 0.0027 0.99
0.025 0.88 0.0064 0.88
-------
other plots investigated, the same trend favoring first
order kinetics is suggested.
. No clear relationship was established between first-
order, .rate coefficients and mean initial oil content for
the data in the first year. This was expected if the re-
action kinetics were in fact first-order and thus in-
dependent of oil concentration.
The average first-order rate coefficients for the
first year is equal to 0.0046 with a standard deviation
of 0.0017. The highest first-order correlation coeffi-
cient correspond to' the rate coefficients for plot 29 and
31 which both showed rate coefficients of approximately
0.003.
Kinetic Rate Evaluation for Second Year
Regression analysis was applied to data from several
plots during the second year of the study, as was done
for a portion of the first years data. In 1983, five
plots were sampled 3-4 times throughout late spring and
summer.
Table 6.6 presents the results of the determination
of kinetic order and rate coefficients for the second
study year. As with the first year data, there is some-
what greater correlation for first order kinetics than
the corresponding zero order values.
An anomaly is present with respect to plot 30. An
increase of 1.2 percent dwb occurred between day 657 and
day 727. No outliers were found in raw oil content data
from these two dates. The anomaly could not be explained
and the correlation coefficient was very low, therefore,
the data from plot 30 was neglected in the determination
of the rate coefficients.
Neglecting the data for plot 30, the mean of the re-
maining four values is 0.0020 with a standard deviation
101
-------
TABLE 6.6. KINETIC ORDER AND RATE COEFFICIENT FOR THE SECOND STUDY YEAR
Plot
4
5
29
30
35
Elapsed
Time
(days)
627
657
727
627
657
727
627
657
727
598
627
657
727
598
627
657
727
Mean Oil
Content
(%dwb)
2.25
1.62
1.44
7.92
7.00
6.59
9.81
9.98
7.84
5.20
4.79
2.51
3.71
7.82
6.40
5.24
4.97
In of
Mean Oil
Content
0.811
0.482
0.365
2.069
1.946
1.886
2.283
2.301
2.059
1.649
1.567
0.920
1.311
2.056
1.856
1.656
1.604
Zero Order? First Order0
Rate . R" Rate R"
0.007 0.74 0.0040 0.78
0.012 0.81 0.0017 0.83
0.022 0.87 0.0025 0.88
0.012 0.32 0.0029 0.24
0.021 0.77 0.0033 0.80
-------
equal to 0.0010.
Assuming non-normal distributions for first-order
for -the first and second year's data, a non-parametric
ranfc: .sum test (Mann-Whitney U-Test) was used to see if
there was any significant difference between the means.
At an a = 0.05 there was found to be no statistical dif-
ference between the first year's mean first-order rate
coefficient of 0.0046 and the second year's coefficient
0.0029.
Zero order and first order coefficients were comput-
ed for eight plots based on two values of the oil content
data taken in 1983 (see Table 6.7). Determination of the
correct kinetic order is not possible on these plots due
to the fact that only two points are available with which
to define the loss curve. The data were taken over a
30-day period and yielded an average first-order coeffi-
cient of 0.0058 with a standard deviation of 0.0039.
Evaluation of Cyclic Loading/Loss Data
An evaluation of the cyclic loading/loss portion of
the 1982 oil content data was made for plots identified
in Table 6.1. In general, the two values of oil content
used to describe each loss cycle were the calculated val-
ue after application.and the final oil content analysis
taken prior to the next oil loading.
The data were clustered into four groups according
to time of the year in which the cycle occurred. This
was done to minimize the effects of differing climatic
and environmental conditions. A summary of the rate co-
efficients for the cyclic loading/loss data is given in
Table 6.8.
A comparison of coefficients was made between groups
to assess the possible effect of differing environmental
conditions. No clear relationships were established
103
-------
TABLE 6.7. RATE COEFFICIENTS FOR 1983 (BASED ON 30 DAY INTERVAL
IMMEDIATELY AFTER APPLICATION)
Plot
9
10
14
15
20
24
25
34
Elapsed
Time
(days)
627
657
627
657
627
657
627
657
627
657
627
657
627
657
627
657
Oil
Content
(%dwb)
3.62
3.05
8.29
6.85
2.70
2.12
8.47
7.88
7.01
5.46
4.55
4.13
1.86
1.33
4.22
4.19
Zero Order
Loss Rate
(%/day)
0.019
0.048
0.019
0.020
0.052
0.014
0.018
0.001
First Order
Loss Rate
(In %/day)
0.0057
0.0064
0.0081
0.0024
0.0083
0.0032
0.0118
0.0002
-------
TABLE 6.8. LOSS RATE COEFFICIENTS FOR CYCLIC OIL LOSS DATA (1982)
o
en
Plot
1
11
26*
2
4
5*
7
9*
13
14
18
20*
25
32
2**
6
7
13
20
25**
32
2
9
Interval
1
1
1
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
4
4
Initial
Oil
Content
10.72
3.74
5.45
4.12
1.55
5.37
3.95
2.16
4.01
1.58
1.39
6.42
1.49
2.58
5.77
11.65
4.84
4.92
7.39
1.69
2.84
6.34
3.10
Final
Oil
Content
9.61
3.23
4.44
3.57
1.31
4.90
3.69
1.99
3.97
1.36
1.04
5.47
1.41
2.18
5.10
10.07
4.54
4.78
6.56
1.55
2.43
5.08
2.98
Number
of
Days
25
24
24
14
14
14
14
14
14
14
14
14
14
14
34
34
36
36
36
34
34
33
33
Zero
Order
(%dwb/day)
0.044
0.021
0.042
0.039
0.017
0.034
0.019
0.012
0.003
0.016
0.025
0.068
0.006
0.029
0.020
0.046
0.008
0.004
0.023
0.004
0.012
0.038
0.004
First
Order
(In %dwb/day)
0.0044
0.0061
0.0085
0.0102
0.0120
0.0065
0.0049
0.0059
0.0007
0.0107
0.0207
0.0114
0.0039
0.0080
0.0036
0.0043
0.0018
0.0008
0.0033
0.0025
0.0046
0.0067
0.0012
(continued)
-------
TABLE 6.8.
(Continued)
O
en
Plot
13
18
26
32
Interval
4
4
4
4
Initial
Oil
Content
5.74
1.79
6.42
3.01
Final
Oil
Content
4.73
1.45
2.77
1.84
Number
of
Days
33
33
33
33
Zero
Order
(%dwb/day)
0.031
0.010
10.111]
0.035
First
Order
(In %dwb/day)
0.0059
0.0064
[0.0255]
0.0149
Determined from hypothetical 'after' value
Determined from measured 'after' value
] Indicates suspect data
-------
based on this data.
Average first-order rate coefficients for the cyclic
load-ing-loss data was found to be 0.0065 with a standard
deviation of 0.0046. The rate coefficients are higher
than those for the first-year as submitted in Table 6.5
or the second year as given in Table 6.6. That the co-
efficients are higher in the period immediately following
application than during later periods suggests that
either some oil fractions are preferentially degraded, or
that loss of oil by some mechanism other than biological
degradation, possibly volatilization, occurs simultan-
eously with biodegradation.
Incorporation of Volatile Emissions in Oil Loss
Data Evaluation
Oil losses due.to volatilization represent a signif-
icant fraction of the total losses. To determine the
magnitude of oil losses via volatilization a study was
performed which is discussed later in this section. The
results are merged with total losses as discussed below
to assess the impact on rate coefficients. Volatile
emissions from five plots were measured as hexane and
computed in terms of oil lost over various time periods
following application. Table 6.9 presents this data.
As a percent of oil applied, the highest losses of
oil due to volatilization occurred following the applica-
tion to plot 4 on September 23, 1982. Total oil lost due
to volatile emissions in 20 days following this applica-
tion was 8.34 kg or approximately 23 percent of the total
oil applied. The greatest net loss of oil between appli-
cations occurred for plot 5 between September 23 and
October 12, 1982. Thirteen kg were lost which represents
a volatile loss of 0.20 percent dwb, approximately half
of the net loss determined by the oil content analysis.
Similarly, for other plots volatile emissions for other
107
-------
plots during a short period of time immediately following
application, accounted for up to 65 percent of the total
losses of oil from a plot. Table 6.10 gives a breakdown
of^tptal and volatile oil losses for several plots.
Rate coefficients were calculated based on total
losses and on total losses minus volatilization which is
considered to be predominately of biological origin.
These results are given in Table 6.11. The removal of
volatile losses from the total losses in the computation
of the rate coefficients had the effect of decreasing the
variance as well as lowering the mean coefficient from
0.0057 to 0.0033. Also, comparing these two values with
those recorded in Tables 6.5 to 6.7, it is interesting to
note that the 0.0033 value closely approximates the mean
value of 0.0046 for the first year and 0.0029 for the
second year taken over a long period after application
and the 0.0057 value corresponds to data taken over a
short period of time immediately after application.
Therefore, the differences in the coefficients determined
from data taken over the cyclic portion of the curves
immediately after application and those determined from a
longer period several weeks after application can
be attributed to the loss of volatile organics.
t
Dormancy Period
As can be seen from several of the figures in Appen-
dix A, a period of low oil loss occurred between day 486
and day 627, as compared to the loss rates following this
period.
The reduction in oil loss rates during the dormancy
period may be due to several factors. This period corre-
sponds to the winter and early spring months between
December and May, and thus low temperature may be partly
responsible for a decrease in biological activity in the
108
-------
TABLE 6.9. TOTAL VOLATILE LOSS FROM FIELD PLOTS
o
vo
Date of
Appl.
07/19/82
08/17/82
09/10/82
10/14/82
11/02/82
11/17/82
Subtotal
07/13/82
08/13/82
09/23/82
10/12/82
11/02/82
11/17/82
Subtotal
07/13/82
08/12/82
09/23/82
10/12/82
11/02/82
11/17/82
Subtotal
Plot
No.
1
1
1
1
1
1
5
5
5
5
5
5
Nominal
Loading
Rate
13
13
13
13
13
13
3
3
3
3
3
3
10
10
10
10
10
10
AppJ.
No.
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Sludge
Applied
(kg)
230.3
230.3
230.3
262.2
262.2
206.53
1421.83
45.31
45.31
60.49
45.31
60.49
47.67
304.58
150.58
150.58
201.67
201.67
262.67
158.86
1125.56
Oil Volatility
Applied of Sludge
(kg) (%)
195.755
195.755
195.755
157.320
157.320
163.158
1065.063
38.513
38.513
36.294
27.186
36.294
37.659
214.459
127.993
127.993
121.002
121.002
157.320
125.499
780.809
_
8.0
7.8
13.6
12.5
9.1
_
8.4
14.0
13.8
12.5
9.1
-
8.5
14.0
13.8
12.5
9.1
Total
Loss
in-2 hr
(kg)
.220
.070
.053
.530
.903
.130
1.906
;070
.063
.340
.100
.260
.056
.889
.150
.090
.810
.320
.330
.130
1.830
Total
Loss
. in-1 d
(kg)
.923
.320
.620
2.550
3.990
.630
97ol3
.390
.386
2.020
.860
1.610
.400
576"66
.720
.600
3.100
1.360
1.820
.650
8.250
Total
Loss
in 7 d
(kg)
3.073
2.090
2.800
6.050
8.700
2.130
24.843
1.910
1.452
6.280
3.230
3.910
1.400
18.182
2.660
2.200
8.150
5.260
5.370
1.850
25.490
Total
Loss
Since
Appl. (kg)
8.173
6.990
11.250
9.790
11.700
4.530
52.433
5.849
4.992
8.340
4.010
5.220
3.800
32.211
7.240
8.390
13.123
11.260
8.290
4.250
527553
Total No.
of Days
Since
Appl.
29
24
34
18
15
33«*
153
31
41
19
20
15
33"
159
30
42
19
20
15
33*«
159
(continued)
-------
TABLE 6.9. (continued)
Date of
Appl.
07/20/82
08/17/82
09/10/82
10/14/82
11/02/82
11/17/82
Subtotal
07/20/82
08/17/82
09/23/82
10/12/82
11/17/82
Subtotal
TOTAL
t Total
% Total
Plot
No.
6
6
6
6
6
6
7
7
7
7
7
Nominal
Loading
Rate
13
13
13
13
13
13
6
6
6
6
6
Appl.
No.*
1
2
3
4
5
6
1
2
3
4
5
Sludge
Applied
(kg)
230.30
230.30
230.30
262.20
262.20
206.53
1421.83
90.62
90.62
121.01
121.01
95.33
518.59
4792.39
Oil
Applied
(kg)
195.755
195.755
195.755
157.320
157.320
163.158
1065.063
77.027
77.027
72.606
72.606
75.310
374.576
3499.97
Volatility
of Sludge
(«)
_
8.0
7.8
13.6
12.5
9.1
_
8.0
14.0
. 13.8
9.1
sludge volatilized:
oil volatilized:
* Application
* No.
d = day
of days
s.
number
from 11/17/82
Total
Loss
in-2 hr.
(kg)
.203
.070
.053
.500
.903
.130
17159
-.110
.045
.560
.130
.093
7938
7.422
.154
.212
Total
Loss
in-1 d
(kg)
1.013
.310
.620
2.510
3.990
.630 '
9.073
.680
.280
3.310
1.000
.510
5.780
37.802
.788
1.080
Total
Loss
in 7 d
(kg)
3.163
2.100
2.800
6.040
8.700
2.130
24.933
2.490
1.700
6.930
3.550
1.610
16.280
109.728
2.289
3.135
Total
Loss
Since
Appl. (kg)
8.263
6.950
11.250
9.780
11.600
4.520
52.343
6.800
5.530
11.110
10.210
4.010
37.660
227.200
4.740
6.491
Total No.
of Days
Since
Appl .
28
24
34
18
15
33**
152
28
37
19
35
33**
1ST
775
to 12/20/82
-------
TABLE 6.10. PORTION OF TOTAL LOSS AS VOLATILE EMISSIONS
Plot
1
4
5
6
7
7
Application
Date
9/10/82
9/23/82
9/23/82
10/14/82
9/23/82
10/12/82
Number of
Days from
Application
to Soil
Sample
25
14
14
34
14
34
Total
% dwb
Lost
1.11
0.74
0.47
1.58
0.26
0.30
Number of
Days for
Volatili-
zation
34
19
19
18
19
35
% dwb
Volatilized
0.172
0.127
0.20
0.149
0.170
0.156
% of Total
Loss Volati-
lized
.15
.17
.42
.9
.65
.52
-------
TABLE 6.11. FIRST ORDER LOSS RATES CORRECTED FOR VOLATILE LOSSES-,-: .
(1) (2) (D-(2)
Initial Oil Oil Content Final No. Total
Plot Oil Volatilized After Oil Days *Biological
Content Volatilization Content
(% dwb) (% dwb) (% dwb) (% dwb) (day )
1 10.72 0.17
4 1.55 0.13
5 5.37 0.20
6 11.65 0.19
7 3.95 0.17
7 4.84 0.16
Mean
10.55 9.61 25 .0044
1.42 1.31 14 .0120
5.17 4.90 14 .0065
11.50 10.07 34 .0043
3.78 3.69 14 .0049
4.68 4.54 34 .0019
.0033
1st Order
Rate Co-
efficient
.0037
.0059
.0038
.0039
.0017
.0009
* Biological - Total minus volatilization
-------
zone of incorporation. In addition to the temperature
effects, saturated conditions existed in most of the test
plots during this time. This high moisture content re-
sulted in anaerobic conditions as evidenced by noxious
odors which were produced when the soil was disturbed.
It was observed that earthworms which had been prolific
in the zone of incorporation prior to the wet weather
were found in large numbers coming to the surface or
floating dead in water on the surface of the plots. Un-
der these conditions biological oxidation of the oil is
extremely limited. A secondary effect of the saturated
conditions was the inability to till the plots which only
compounded the problem.
FRACTIONATION STUDIES
An investigation into the fate of four oil fractions
was performed for plots 30 and 35 which had received mod-
erate sludge loadings. Samples were fractionated into
asphaltenes, saturates, aromatics, and polar compounds.
The methodology used for fractionating the sludges and
recovered oils was discussed in Section 5.
Since the oil was fractionated prior to application,
the relative amounts of each fraction applied was known.
Amounts of the total oil and the individual fractions ap-
plied to each study plot are given in Table 6.12. As can
be seen from this table, the first two applications to
each plot were made with the same batch of sludge (Batch
I) and the third application was made using a different
sludge (Batch IV).
Oil recovered from soil samples taken from the zone
of incorporation was fractionated and calculated as a
weight percent of the recovered oil. The raw fraction-
ation data is presented in Table A.4, Appendix A. There
were three samples for fractionation for each sample
113
-------
TABLE 6.12. AMOUNTS OF OIL AND OIL FRACTIONS
APPLIED TO PLOTS 30 and 35
Plot
No.
30
30
30
35
35
35
Elapsed
Day
0
151
486
0
151
486
Applied
Oil
(% dwb)
3.85
6.90
3.45
6.15
6.81
5.75
% Asph.
In Oil
(%)
1.50
1.50
4.43
1.50
1.50
4.43
% Asph.
In Soil
(% dwb)
0.06
0.10
0.15
0.09
0.10
0.25
% Sat.
In Oil
(%)
60.50
60.50
30.15
60.50
60.50
30.15
% Sat.
In Soil
(% dwb)
2.32
4.17
1.04
3.72
4.12
1.73
* Arom .
In Oil
(*)
27.90
27.90
37.15
27.90
27.90
37.15
% Arom.
In Soil
(% dwb)
1.07
1.93
1.28
1.72
1.90
2.14
% Pol.
In Oil
(%)
10.10
10.10
28.26
10.10
10.10
28.26
% Pol.
In Soil
(« dwb)
0.39
0.70 '
0.98
0.62
0.69
1.62
-------
date. Mean values were computed for each sample after
deleting any outliers. Mean values are given in Table
6.13,
.Sludge loadings to plots 30 and 35 were made on
1 V
elapsed day. 0, 151, and 486. Soil analyses were per-
formed on days listed in Table 6.13. Based on the avail-
able data, total losses for each fraction were computed
for two periods. The first period was from the first day
through day 486 (prior to the third sludge application).
The second period was from day 486 to day 657. Losses
for the first period were computed based on the sum of
the first two loadings and the analysis of day 486. The
total losses for the second period were computed as the
sum of the residual concentration of each fraction based
on the analysis for day 486 plus the loading of that day
minus residual for day 657. Total loss data are summar-
ized in Table 6.14.
As can be seen from Table 6.14, the highest total
loss during the first period for both plots occurred for
the saturates fraction, followed by aromatics, polar com-
pounds and asphaltenes. First period losses as a per-
centage of the total applied and calculated as shown in
Table 6.14 were highest for saturates followed by aro-
matics, asphaltenes, and polar compounds. It should be
noted that the first period losses for most fractions
were fairly high due to the fact that the sludge applica-
tions were made in the first five months of the sixteen
month period.
Second period losses were found to differ substan-
tially from those of the first period. The most surpris-
ing difference was the decrease in the losses of the sat-
urates fraction. All fractions with the exception of
polar compounds showed lower losses during the second
period than the first. The relative magnitude of the
115-
-------
TABLE 6.13.
MEAN CONCENTRATIONS OF OIL FRACTIONS -
PLOTS 30, 35.
Elapsed
Day
385
401
444
486
598
627
657
385
401
444
466
598
627
697
Oil
In
Soil
(%dwb)
4.50
3.15
2.85
1.94
5.20
5.10
2.51
5.38
4.37
3.87
2.48
8.70
6.52
5.24
Asph.
In
Soil
(%dwb)
0.21
0.19
0.25
0.07
0.28
0.30
0.11
0.34
-
0.34
0.11
0.54
0.45
0.28
Sat.
In
Soil
(%dwb)
2.10
1.28
0.86
0.34
1.65
-
0.84
2.25
1.90
1.09
0.92
3.23
-
2.17
Arom.
In
Soil
(%dwb)
1.38
0.89
0.77
0.68
1.37
-
0.74
1.36
-
0.98
0.88
1.76
-
1.12
Pol.
In
Soil
(%dwb)
0.81
0.79
0.96
0.74
1.90
-
0.87
2.29
1.62
1.45
0.95
3.01
-
1.67
116
-------
TABLE 6.14. TOTAL LOSSES OF OIL FRACTIONS
Plot 30
Period 1 Period 2
Oil :; = =
Applied
Sample
Oil
Oil
Loss
% Loss
Asphalt
Applied
Sample
Asphalt
Asphalt
Loss
% Loss
Sat.
Applied
Sample
Sat.
Sat.
Loss
% Loss
Arom.
Applied
Sample
Arom.
Arom.
Loss
% Loss
10.75
1.94
8.81
82
0.16
0.07
0.09
56
6.49
0.34
6.15
95
3.00
0.68
2.32
77
3.45
2.51
2.88
53
0.15
0.11
0.11
50
1.04
0.84
0.54
39
1.28
0.74
1.22
62
Plot
Period 1 "
12.96
2.48
10.48
81
0.19
0.11
0.08
42
7.84
0.52
7.32
94
3.62
0.88
2.74
76
35
Period 2
5.75
5.24
2.99
36
0.25
0.28
0.08
24
1.73
2.17
0.08
4
2.14
1.12
1.90
63
(continued)
117
-------
TABLE 6.14 (continued)
Plot 30
Period 1 Period 2
Pol.3
Applied 1.09 0.98
Sample
Pol. 0.74 0.87
Pol.
Loss 0.35 0.85
% Loss 32 49
Plot 35
Period 1 Period 2
1.31 1.62
0.95 1.67
0.36 0.90
27 35
*
All values % dwb in soil unless specified.
118
-------
individual fraction losses were highest for aromatics
followed by polar compounds, asphaltenes and saturates.
Losses of polar compounds increased for both plots during
the.:, second period. The second period was only
approximately 170 days consisting of approximately four
months of relative dormancy during which time the cold
weather and saturated conditions were responsible for low
overall oil losses.
The composition of the sludge applied just prior to
the second period was also different than that applied
during the first period. The saturates content of Batch
IV was less than half that of Batch I, and as compared to
Batch I, all of the other fractions were from 33 to 295
percent higher.
Anomalous increases in concentration of asphaltenes
(pentane insoluble compounds), saturates, and polar com-
pounds were found following the third application of
sludge. Although these increases were not expected they
can be explained and have been noted by other researchers
(Meyers and Huddleston, 1979). The time period during
which the increases occurred, coincided with cold weather
and saturated soil conditions. Therefore, anoxic con-
ditions existed with a possibility of anaerobic decompo-
sition.
Walker et al., (1976) characterized the pentane
insoluble fraction using computerized mass spectrometry
as carboxylic acids, ketones, esters and porphyrins.
Waksman (1927) has shown that anaerobic decomposition
produces various acids, such as acetic, butyric and
lactic, and alcohols, such as ethyl and butyl and in some
cases acetone. Ojinsky and Umbreit (1959) showed that
the anaerobic decomposition of aromatic ring compounds
produces acids, saturated hydrocarbons, alcohols and
ketones. Evans (1977) delineated the anaerobic decompo-
119-
-------
sition of the benzene nucleus under three different sets
of biological conditions. The three conditions are:
anaerobic photometabolism of benzoate by Athiohodaceae,
anaerobic metabolism of dichlorophenol, giving rise to
quinolines; and quinolines observed in the presence of
fungal phenoloxidase in soil (Liu et al., 1981, Rosazza
1982).
During the time period when an increase in polar
compounds was seen, phenol, 2 nitrophenol and penta-
chlorophenol, as well as benzene, nitrobenzene, and iso-
i
phorone, were detected in the soil matrix.
Nonenzymatic transformation of aromatic and phenolic
compounds into other polar compounds, such as xenobiotic
compounds, is also possible, due to the alteration of the
physico-chemical environment by variations of pH, temper-
ature, redox potentials and other factors (Rosazza). En-
zymatic conversion of organic sulfur compounds to sulf-
oxides in sterile soils were observed (Chin et al., 1970,
Rosazza 1982) . Sulfoxidation of carboxin by the fungus
Utilago mayolis was observed in the soil by Lyr et al.,
(Rosazza 1982) .
Thus, the relatively low apparent losses of polar
compounds may be due to the production of these compounds
as by-products of the degradation of saturates and other
compounds as has been suggested by several researchers.
The complex and dynamic nature of the microorganism popu-
lation, and the complex nature of the organic substrates
contained in the sludges makes evaluation of the actual
degradation rates very difficult. Thus, the losses re-
ported in Table 6.15 and loss rates as discussed below
and recorded in Table 6.16 only reflect the apparent net
losses.
First-order rate coefficients were computed for both
periods. First period coefficients were based on data
120
-------
TABLE 6.15. TOTAL OIL AND OIL FRACTION LOSSES
Oil Applied
Sample
Loss
% Loss
Asph. Applied
Sample
Loss
% Loss
Sat. Applied
Sample
Loss
% Loss
Arom. Applied
Sample
Loss
% Loss
Pol. Applied
Sample
Loss
% Loss
Plot 30
14.2
2.51
11.69
82
0.31
0.11
0.20
65
7.53
0.84
6.69
89
4.28
0.74
3.54
83
2.07
0.87
1.20
58
Plot 35
18.71
5.24
13.47
72
0.44
0.28
0.16
36
9.57
2.17
7.40
77
5.76
1.12
4.64
81
2.93
1.67
1.26
43
TABLE 6.16. FIRST-ORDER RATE COEFFICIENTS FOR OIL
FRACTIONS
Plot
30
30
35
35
Period
1
2
1
2
Rate
Coefficient
Asph.
0
0
0
0
.0310
.0160
.0260
.0110
0
0
0
0
Sat.
.0170
.0114
.0140
.0104
0
0
0
0
(K) (day
Arom.
.0059
.0097
.0040
.0086
-1
0
0
0
)
Pol.
-
.0130
.0055
.0104
121
-------
taken during the last one-hundred days of the 486 day pe-
riod. Coefficients for the second period were developed
from, data taken after the winter dormancy period. The
firs't-order coefficients for each fraction by plot and
study period are given in Table 6.16. As can be seen
from this table, the coefficients for the first period
were higher for the saturates and asphaltenes fractions
than the corresponding second period values, with aromat-
ics and polar compounds having higher coefficients in the
second period. Comparing plots 30 and 35 it is interest-
ing to note that as the total oil applied increases the
net loss also increases which is consistent with data
from all other plots. However, the efficiency and the
rate coefficients decrease with increasing oil concentra-
tions. The decrease in efficiencies is explainable in
that efficiencies for all waste treatment systems is a
function of loading rates i.e., efficiency decreases with
a increase in loading rate. The coefficients for plot 30
were 10-45 percent higher than the corresponding values
for plot 35. This trend is not supported by data from
the other plots. As stated previously there was no
relation between rate coefficients and oil concentra-
tions. It was noted that rate coefficients were highest
for asphaltenes, followed by saturates, polar compounds
and aromatics.
Asphaltenes show greater rate coefficients than
other fractions because as the asphaltenes degrade other
fractions were formed. Whereas, the other fractions,
even though they degrade, were being produced as degrada-
tion products of asphaltenes, thereby showing a lower co-
efficient. The asphaltenes (measured as pentane insol-
uble compounds) produced during anoxic conditions were
probably carboxylic acids, ketones, esters, aldehydes and
alcohols (Walker et al., 1976). Therefore, as soon as
122
-------
the plots were tilled after the anoxic period, there was
an immediate and rapid depletion of all compounds, which
were/readily amenable to degradation under aerobic con-
ditions .
The above results of oil content and fractionation
show that oil and the associated fractions degraded with
time. The degradation of oil and fractions occurred pre-
dominantly in the summer and fall months. An inhibition
period was observed during winter months, when there was
no appreciable degradation for total oil content - even
though the individual fractions showed increases and de-
creases.. During the winter months saturates, asphaltenes
and polar compounds showed increases. The increases were
due to the anaerobic decomposition of oil. However, aro-
matics were found to degrade into other fractions even
during winter months. Asphaltenes and polar compounds
were found to degrade with time; which is contrary to the
studies reported in the literature.
The oil losses for this study was found to be in
agreement with that reported in the literature (Table
6.17). The loss of fractions presented in Table 6.18
ranged from 36 to 39 percent for the two year period.
UNSATURATED ZONE MONITORING
The results of the oil content analysis in the un-
saturated zone are presented in Table 6.19. The results
show that there was no significant migration below the
zone of incorporation. The results of the oil content on
elapsed day 231 (4/7/82) , show that at a depth of from
30-40 cm (12-16 in) the oil concentration was in the
range of 0.13 to 0.63 percent dwb. Inclement weather
conditions did not permit the tilling of the plots and
may have led to some vertical oil migration. However,
analysis of the unsaturated zone at the end of 406 days
123
-------
TABLE 6.17. OIL LOSSES - COMPARISON WITH REPORTED VALUES
Reference
Huddleston and Myers
Raymond et al.
Present study
TABLE 6.18. OVERALL
Oil Applied
Sample
Loss
% Loss
Asph. Applied
Sample
Loss
% Loss
Sat. Applied
Sample
Loss
% Loss
Arom. Applied
Sample
Loss
% Loss
Pol. Applied
Sample
Loss
% Loss
% Oil Losses/Year
72
485-90
45-81
LOSSES OF OIL FRACTIONS
Plot 30
14.2
2.51
11.69
82
0.31
0.11
0.20
65
7.53
0.84
6.69
89
4.28
0.84
6.69
83
2.07
0.87
1.20
58
Plot 35
18.71
5.24
13.47
72
0.44
0.28
0.16
36
9.57
2.17
7.40
77
5.76
2.17
7.40
81
2.93
1.67
1.26
43
124
-------
TABLE 6.19. OIL CONTENT ANALYSIS OF THE
UNSATURATED ZONE
Plot NO.*
30-1
30-2
35-1
35-2
30-1
30-2
35-1
35-2
35-3
35-4
30-1
30-2
35-1
35-2
Depth of
Sampling
30-40 cm
30-40 cm
30-40 cm
30-40 cm
91-107 cm
152-163 cm
61-71 cm
86-102 cm
117-132 cm
152-163 cm
61-76 cm
97-107 cm
61-76 cm
107-122 cm
Date
4/7/82
4/7/82
4/7/82
4/7/82
9/30/82
9/30/82
9/30/82
9/30/82
9/30/82
9/30/82
7/15/83
7/15/83
7/15/83
7/15/83
Oil Content Wt. %
on Dry Wt. Basis
0.13
0.29
0.33
0.63
0.04
0.03
0.05
0.02
0.09
0.03
0.20
0.15
0.15
0.05
The 1 and 2 after the plot no. represent duplicate
samples.
125
-------
shows that the oil content values below 40 cm were sim-
ilar to the background oil levels.
VOLATILE EMISSIONS FROM LAND TREATMENT OF PETROLEUM RESI-
DUES.; .
The atmospheric emissions from land treatment of pe-
troleum sludge were assessed in this study. This section
presents analyses and results. The first part is a sum-
mary of the sniffer data for laboratory and field experi-
ments. The second part presents the results of statis-
tical analyses. The third part shows the significance of
results from the standpoint of air pollution. The fourth
part presents the results and interpretation of the gas
chromatography data.
LABORATORY AND FIELD STUDIES
Stripping Tests
Stripping tests were carried out to measure volatil-
ity of the sludge and to estimate weight loss of indi-
vidual sludge components due to volatilization from land
treatment operations. The procedures have been described
in Section 5.
Hydrocarbon concentrations in the stripping gas were
monitored every five minutes and weight loss of sludge
was measured every ten minutes during at least a two-hour
test run. Because of differences in volatility of the
different batches of sludge, a stripping test was con-
ducted each time the application was made. The volatil-
ity of these sludges was calculated and is presented in
Table B.I, Appendix B. Table 6.20 presents the stripping
test results for the last batch of sludge. This sludge
was also used for laboratory experiments. In this test
air was purged into the sludge sample at 2.02 1/min.
These data were used to construct curves of cumulative
calculated TLV Sniffer responses as a function of time
126
-------
TABLE 6.20. STRIPPING TEST RESULTS
to
Stripping
Time (min.)
<1
5
10
15
20
25
30
40
45
50
55
60
65
70
80
90
100
110
Reading
Direct
(ppm)
3200
2000
1500
1200
1000
900
600
380
310
300
230
190
140
110
80
30
20
from sniffer
Calculated
(mg/min. )
22.76
14.23
10.67
8.54
7.11
6.40
4.27
2.40
2.21
2.13
1.63
1.35
.99
.78
.57
.21
.14
Area
Count
37
20.5
14.5
9.0
5.5
4.0
3.0
1.9
1.0
.7
.2
Mass of
Volatiles
(ing)
148
82
58
36
22
16
12
7.6
4.0
2.5
.1
Cummulative
Mass
(mg)
148
230
288
324
346
362
374
381.6
385.6
388.1
388.1
Wt**
Loss
(mg)
278.4
169.3
154.8
87.3
85.3
65.0
61.7
36.7
8.3
4.5
3.9
Cmjimulative
Wt* Loss
(mg)
278.4
447.7
602.5
689.8
775.1
840.1
901.8
938.5
946.8
951.3
955.2
* Air flow through the sludge = 2.02 1/min.
** Initial wt. of sludge = 11045.3 g
% wt. loss of sludge =8.5
-------
and sludge weight loss (Figures 6.3 and 6.4). These
curves can be used to relate the emission rate to the
weight loss for other experimental tests using the same
sludge.
As might be expected, the rates of emission and
weight loss were time-dependent. For example, the ini-
tial weight loss rate was 278.4 mg/10 min. and declined
to about 3.9 mg/10 min. within 110 minutes. During the
same period the volatile losses measured by the Sniffer
was 22.76 mg/min. initially and dropped to 0.14 mg/min.
after 100 minutes. The percentage of weight lost during
a 110 minute test period for the last batch of sludge,
was calculated to be 8.65 percent.
In view of the results obtained, it was decided to
conduct an experiment with water under the same condi-
tions as the sludge sample to estimate water loss. Dur-
ing the test period, the water loss was insignificant
(approximately 0.12 percent) compared to the volatile-
loss.
Total Volatile Emission
Throughout the sampling and testing period, the lab-
oratory and field analytical results were transferred to
a master log. The data was then stored on a tape in an
IBM computer system. Preparation of the raw data into
usable form involved converting ppm reading from sniffer
to g/hr of total volatiles. Tables B.I and B.2 in Appen-
dix B present calculated concentrations of total volatile
hydrocarbons for field and laboratory experiments. From
these data, calculated concentration-time plots, such as
those shown in Figures 6.5 and 6.6, were generated. The
patterns observed in these graphs are typical of all
loading rates and all temperature ranges, although the
emission rates at any time vary with loading rates and
environmental conditions.
128
-------
c
c
o
E O
ul *
c *
I ?
'
K)
VO
3
u
230
160
100
10 2O 3O 40 60 00 7O 80 SO 100 110
Tim* (mln)
Figure 6.3. Calculated total volatile emission of sludye
sample vs time.
-------
u>
o
~ aoo
600
400
aoo
200
E
u too
20.14
% Cumulative weight loss
46.84
03.07 72.21 01.14
04.40
07.06 00.60
tOO 200 300 400
600
000 700 600 000 1000 1100
Figure 6.4
Cumulative weight loee el eludge (ing)
Relationship between cumulative total volatile mass
and sludge weight loss.
-------
During Application
300
Loadlng Rate = 3%
Loading Rat* = e%
Loading Rate = 10%
Tamparalur* aO*F
CM
e
24
48
72
96 120
Tim* (Hour*)
Figure 6.5.
The effect of loading rate and tilling frequency
on emission in laboratory experiments at 60°F.
-------
400-1
u>
10/12
3 4
10/14 10/16
Tim* (Day*) Sampling 0*1*
-------
These figures, show that in the laboratory a very
sharp rise in the hydrocarbon concentration in the air
appeared immediately after sludge application began. The
maximum hydrocarbon concentration was reached during the
application or very shortly thereafter. However, an ab-
rupt decline from the maximum concentration and a gradual
approach to a lower concentration followed. These re-
sults are similar to the results achieved by Minear
et al. (1981) .
In the field, because of losses which occurred dur-
ing sludge application, and the time which elapsed before
the chamber could be placed over the soil after applica-
tion, a more gradual rise in hydrocarbon concentration
was noted in the sampling chamber.
The hydrocarbon concentration in most tests dropped
to less than 50 percent of its maximum value within two
hours after application. Therefore, it was evident that
comparisons of the concentrations for the first two hours
and for the first day would give a quick estimation of
the relative hydrocarbon emission losses. Figures 6.7
and 6.8 show the maximum concentration and rate of de-
crease in emission in the first two hours from applica-
tion at three different temperatures and loading rates.
The areas under the time-concentration curves were
determined at two hours, one day and seven day intervals
from application for field and laboratory data, and from
application to application for field data only. From
these areas the losses were calculated for each loading
rate. Table 6.21 gives the summarized data by plot
number and loading rate for all the samples collected
from the field plots. This table can be used to obtain
an estimate of volatile losses at various time intervals
and sludge loading rates. Included in the table are the
date of application of sludge, percent volatility of
133
-------
400 H
300
u>
o
CD
S
a
I
I
200
Loading Rat* = 3%
Loading Rale 0%
Loading Rala - 10%
100-1
Temperature
36*F
Temperature = eo*F
eo 120
Tint* (mlnuloa)
60 120
Time (mlnulea)
Figure .6.7. Rate of emission of volatiles in first two hours
after application at temperature 35°F and 60°F.
-------
Loading Rat* = 3%
Loading Rat* = 6%
Loading Rat* = 10%
T*mp*ratur* 86*F
Figure 6.8. Rate of emission of volatiles in first
two hours after application at temper-
ature 85°F.
135
-------
TABLE 6.21. TOTAL VOLATILE LOSS FROM FIELD PLOTS
10
Date of Plot Nominal
Appl. No. Loading
Rate
07/19/82
08/17/82
09/10/82
10/14/82
11/02/82
11/17/82
Subtotal
07/13/82
08/13/82
09/21/82
10/12/82
11/02/82
11/17/82
13
13
13
13
13
13
3
3
3
3
3
3
Subtotal
07/13/82 5 10
08/12/82 5 10
09/23/82 5 10
in/12/82 S 10
11/02/82 5 10
11/17/82 5 10
Subtotal
Appl,
No.
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
S
6
Sludqe
Appl led
(kq)
230.3
230.3
230.3
262.2
2fc2.2
206.53
14TTTJ
45.31
4S.31
60.49
45.31
60.49
47.67
304.58
150.58
150.58
201.67
201.67
262.67
158.86
1125.56
Oil Volatility
Applied of Sludge
(kgl (t)
195.755
195.755
195.755
157.320
157.320
163.158
1065.06)
38.513
38.513
36.294
27. 186
36.294
37.659
214.459
127.993
127. 99J
121 .002
121 .002
157. )20
125.499
780.809
_
8
7
13
12
9
_
8
14
13
12
9
.
8
14
13
12
9
.0
.8
.6
.5
.1
.4
.0
.8
.5
.1
.5
.0
.8
.5
.1
Total
Loss
in-2 hr
(kg)
.220
.070
.053
.530
.903
. 130
17506"
.070
.063
.340
.100
.260
.056
7889
.150
.090
.810
.320
.110
.1 JO
1 .810
Total
Loss
. in-1 d
(kgl
.923
.320
.620
2.550
3.990
.610
975TJ
.390
.386
2.020
.SCO
1.610
.400
5.666
.720
.600
). 100
1 . 360
1 .B20
.6',0
8. 210
Total
Loss
in 7 d
(kq)
3.073
2.090
2.800
6.050
8.700
2. 130
2T7Fn
1.910
1.452
6.280
3.230
3.910
1.400
187113
2.660
2.200
8.150
5.260
5. 370
1 .850
25.490
Total
Loss
Since
Appl. (kq)
8. 173
6.990
11.250
9.790
11.700
4.5)0
sTrm
5.849
4.992
8.340
4.010
5.220
3.800
32.211
7.240
8.390
13. 123
11.260
8.290
4.250
52.553
Total No.
of Days
Since
Appl.
29
24
34
18
15
33"
in
31
41
19
20
15
33"
159
30
42
19
20
15
31"
r>9
(continued)
-------
TABLE 6.21. (continued)
U)
bate of
Appl.
07/20/82
08/17/82
09/10/82
10/14/82
11/02/82
11/17/82
Subtotal
07/20/12
08/17/82
09/23/82
10/12/82
11/17/82
Subtotal
TOTAL
1 Total
1 Total
Plot
No.
6
6
6
6
6
6
7
7
7
7
7
ludqe
Nominal
Loading
Rate
13
13
13
13
13
13
6
6
6
6
volatilized:
Appl.
No.
1
2
3
4
5
6
1
2
3
4
5
Sludge*
Appl icd
Ikgi
230.30
2J0.30
230. 10
262.20
262.20
206.53
90.62
90.62
121.01
121 .01
95.31
sTe ."59
4792.39
Oil Volatility
Applied of Sludge
Ik.jl IM
195.755
195. 755
195.755
157.320
157. 120
163. 158
10~6b.U63
77.027
77.027
72.606
72.606
75.JJO
3499.97
_
H.O
7.8
1 1.6
12.5
9. 1
.
8.0
14.0
11.8
9.1
oil volatilliedi
Total Total
Loss Loss
in-2 hr . in- 1 d
(kg) (krjl
.203
.070
.051
.500
.903
. 130
iTSTf
.110
.045
.560
.130
.093
.918
7.422
.154
.212
1.013
. 310
. t>20
2 . ', \ 0
3.990
.6 10
97(573'
.680
.280
3. 110
1 .000
.510
37.802
. 788
I.U80
Total
I(IS3
in 7 d
Ikql
3.163
2.100
2.800
6.040
8.700
2.130
2T79T1
2.490
1.700
6.930
3.550
1.610
16T7B75
109.728
2.289
3.135
Total
Loss
Since
Appl. fkcj)
8.263
6.950
11.250
9.780
11.600
4.520
5I7TT3
6.800
5.530
11.110
10.210
4.010
J7.66&
227.200
4.740
6.491
Total No.
f> I Days
Sin.-c
Appl.
28
24
34
18
15
33"
28
37
19
35
33"
775
Application number
No. of days from 11/17/82 to 12/20/82
daya
-------
sludge, the amount of sludge and equivalent oil applied
each application, the calculated losses at different
times, and the total number of days between applications.
]..During a six-month test period in the field (July 13
- December 20, 1983) total volatile losses for each plot
individually, and for all five plots combined, were also
2
calculated. The volatile loss is given in kg/16.7 m
»«\
(180 ft") of plot area.
The results indicate that of the 4792 kg (10560 Ib)
of sludge applied to plots 1,4,5,6 and 7, 3500 kg was
oil. During the six months following the first applica-
tion, 4.7 percent was lost through volatilization to the
atmosphere which is equivalent to 6.5 percent of the
total oil applied. The percentage of loss, estimated on
the basis of total sludge and total oil applied, is given
in Table 6.21. The total percentages of losses in two
hours, one day and seven days from application were esti-
mated at .15, .79 and 2.29, respectively. Since the loss
rate decreases with time, the percentage of loss in about
six months was found to be approximately twice the per-
centage of loss in seven days from application.
The percentages of total loss in two hours, one day
and seven days from application were also calculated on
the basis of total loss over the 152 to 159 day period.
The results are presented " in Table 6.22. Figure 6.9,
generated from Table 6.22 also shows the percentage of
total loss as a function of time for different loading
rates. Approximately 50 percent of total volatiles was
lost in seven days after application from each plot.
Therefore, the seven-day period chosen for laboratory
experiments was an adequate time period to use in
comparing the effects of variables on emission.
From Table 6.21 it is evident that the higher load-
ing rates resulted in higher volatile losses, assuming
138
-------
OJ
10
TABLE 6.22. PERCENT OF TOTAL LOSS FROM DIFFERENT LOADING
RATES AT DIFFERENT TIMES FROM APPLICATION
Plot 1
4
7
5
1
6
% Loading
Rate
3
6
10
13
13
Total 1 *
of days
159
152
159
153
152
Total
Loss
kg
32.211
37.660
52.553
52.433
52.343
% of
two hours
2.75
2.49
3.48
3.63
3.55
Total Loss
one day
17.59
15.34
15.69
17.22
17.33
in
seven days
56.44
43.22
48.50
47.38
47.63
Total I of days that total losses were calculated for each plot starting
from first application (7/13/1982-7/20/82) to the last sampling date
(12/20/82).
-------
*>.
o
o
«
*
100
90
80
ro
60
60
40-
30
20-
10
Loading Rata -3%
Loading Rat* - e%
Loading Ral« - 10%
Loading Rala - 13%
1 2 3
Application
Figure 6.9.
4667 *
162 163
160
Tlma (Oaya)
Percent volatile loss at different loadino
rates vs time.
-------
all other conditions were constant. However, losses from
plot 5 were higher than expected for two reasons. First,
there was a misapplication on 11/2/82 of 262 kg (13 per-
cent.; loading rate) instead of 206 kg (10 percent loading
rate). The second reason was that on 9/23/82 application
to plot 5 was made from a new batch of sludge with high
volatility (14 percent), while on 9/10/82 old sludge with
low volatility (7.8 percent) was applied to plots 1 and
6. These facts have resulted in about 4-5 kg more vola-
tile loss from plot 5 than expected. Occurrences of this
kind compound the problems of predicting volatile losses.
The range of total volatile loss was from a low of 3.80
to a high of 13.12 kg. The arithmetic means and standard
deviation of total loss for each plot separately and all
five plots together are presented in Table 6.23.
Another important discovery (Table 6.21) was the
variation of volatile losses within each loading rate
from one application to another. This variation could be
explained primarily on the basis of volatility of differ-
ent batches of sludges. It was found that volatility of
the sludge is a very important factor in determining
emission rates. For this reason a stripping test was de-
veloped in an attempt to provide a quantitative measure
of relative volatility which could be related to emission
rates. The method was described in Section 5, and the
results of one stripping test were presented earlier in
this section. Besides volatility, environmental con-
ditions such as soil temperature, soil moisture content
and relative humidity contributed to these variations.
Monitoring of volatiles in the field was continued
on 4/19, 5/9 and 6/19, 1983. The last application on the
plots was on 11/17/82. On 5/9 and 6/19, 1983 a higher
rate of emission was observed (Table B.I, Appendix B)
than on 12/20/82. This could be due to higher soil mois-
141
-------
to
TABLE 6.23. MEAN AND STANDARD DEVIATION OF TOTAL AMOUNT OF
SLUDGE APPLIED AND TOTAL VOLATILE LOSS
Effective Plot Nominal Weight Mean/ Std. Weight Total Mean/ Std.
Date 8 Loading Sludge APP Dev. Oil Volatile APP Dev.
(1982) Rate Applied, Applied Loss/kg
kg (six appl.)
7/13-12/20 4 3 305
7/20-12/20 7 6 519
7/13-12/20 5 10 1126
7/19-12/20 6 13 1422
7/20-12/20 6 13 1422
Totals 4794
APP = Application
50 8.0 214 32.2 5.37 1.65
104 15.9 375 37.7 7.53 3.04
188 43.7 781 52.6 8.76 3.11
237 21.6 1065 52.4 8.74 2.73
237 21.6 1065 52.5 8.75 2.73
163 3500 227.4 7.84
-------
ture content and elevated temperatures in May-June 1983
than in December 1982.
.As previously discussed, the laboratory experiments
were.; conducted in controlled environmental conditions to
investigate the effects of loading rate and temperature
on the rate of emissions of volatiles. The procedures
and conditions for conducting these experiments were dis-
cussed in Section 5. Since it was difficult to evaluate
statistically the effects of relative humidity and soil
moisture content from field data because of insufficient
data for those two parameters, two separate studies, one
with high soil moisture content (23 percent) and the
other with high relative humidity (75 percent), were per-
formed in the laboratory. The soil temperatures for both
tests were held constant at 60°F. One loading rate (6
percent) was tested with high soil moisture content,
while two different loading rates (6 and 10 percent) were
studied with high relative humidity.
The calculated rates of emissions for laboratory ex-
periments are presented in Table B.2, Appendix B.. From
these data using the same methodology as for field data
recorded in Table 6.21, the data in Table 6.24 were
generated. Based on these data, the effects of loading
rate, soil temperature, relative humidity, soil moisture
content and tilling on emissions were determined.
The Effect of Loading Rate on Emissions
Three different loading rates (3, 6 and 10 percent)
were examined in the laboratory at three temperature
ranges. The results from laboratory experiments con-
firmed the field results; i.e., higher mass emission was
achieved at higher loading rates. The relationship be-
tween emission rates and different loading rates of
sludge is shown in Figures 6.5, 6.10 and 6.11. From
143
-------
TOTAL 6.24,
TOTAL VOLATILE LOSS FROM LABORATORY EXPERIMENT
Date
of
Appl.
3/31/83
5/16/83
6/1/83
4/4/83
5/17/83
6/1/83
4/1/83
5/24/83
6/3/83
6/10/83
7/5/83
7/5/83
Loading
Rate
(1)
3
3
3
6
6
6
10
10
10
6
6
10
Soil
Temp.
CF)
35
60
85
35
60
85
35
60
83
60
60
60
Soil
Moist.
Content
II)
12
12
12
12
12
12
12
12
12
23
12
12
Relative
Humidity
III
52
52
52
52
52
52
52
52
52
52
70
70
No. of
Tilling
2
2
2
2
2
2
2
2
2
2
2
2
Amt.*
Sludge
Aj>p 1 1 cd
(kg)
41.746
41.746
41.746
82.040
82.040
82.040
133.960 '
1)3.960
1)3.960
82.04
82.04
1)3.96
Amt . »
Oil
Applied
(kg)
26.30
26.30
26.30
51.68
51.68
51.68
84.39
84.19
84.39
51.68
51.68
84.39
Total
Loss
in 2-hr.
(kg)
.243
.335
.350
.))0
.367
.388
.4)3
.473
.622
.550
.300
.400
Total
Loss
in 1-d
(kg)
.90
1.10
1.30
1.00
1.40
1.90
1.15
2.65
2.90
2.40
.80
1.50
Total
Lor. s
in 7-d
Ikg)
2.35
2.50
4.15
2.75
3.90
5.60
3.15
5.60
7.00
7.60
2.30
3.50
Max
Emission
Rale
g/hour
204.762
307.144
511.906
307.143
375.397
546.0)3
2)8.889
375.397
580.160
511.906
341.270
341.270
Volatility of iludge was 8.5% and density of sludge was .90 g/ml
Amount of oil based on the 63* oil in sludge determined by Extraction Method
-------
400
c
o
300
Loading Rala 3%
Loading Rata « 0%
Loading Rat* - 10%
Tamparatura 36*F
MO
cn
100-
1
Application
24
t
48
t
T2
ee
120 146
Tbna (Hours)
170
104
218
Figure 6.10. The effect of loading rate and tilling frequency on
emission in laboratory experiments at 35°F.
-------
eoo-i
Loading Rale
Loading Ral«
Loading Rala
= 66'F
3%
6«
10%
24 46
APPLICATION
120 146 170
Tint* (Hour*)
242 266
Figure 6.11o The effect of loading rate and tilling frequency on
emission in laboratory experiments at 85°F.
-------
these figures and data in Table 6.24, it can be seen that
highest emission rate was achieved at 10 percent loading
rate, for all temperature ranges.
The -Effect of Soil Temperature on Emissions
As would be expected, the volatilization rate was
strongly affected by temperature changes. The higher the
temperature, the higher the vapor pressures of volatile
compounds and the greater was the amount of volatiles
emitted. Figures 6.12 - 6.14 illustrate the effect of
three temperatures (35°F, 60°F, 85°F) at three different
loading rates on the rate of emission of volatiles. A
trend can be observed for each temperature within one
loading rate. Temperature, in addition to its effect on
vapor pressure, may also affect such factors as desorp-
tion, diffusion to the surface and rates of water loss -
all factors that can contribute to the overall rate of
loss of volatiles from a soil system. Total seven day
loss as a function of variable temperatures and loading
rates is shown in Figure 6.15.
Effect of Relative Humidity on Emissions
In all except two experiments, the relative humidity
was maintained at 52 percent. Two experiments, one with
6 percent and the other with 10 percent loading rate,
were made at 75 percent relative humidity. Soil tempera-
ture in these two studies was held at 60°F. The results
of these experiments are given in Table B.2, Appendix B
and Figure 6.16. As shown in Figure 6.16 there were
slight differences in volatilization immediately after
sludge application with increased relative humidity.
However, later there was a marked decrease in the rate of
emission. This is because of the fact that the initial
rate of volatile loss of compounds from soil is primarily
a function of the concentration of the volatiles at the
147
-------
00
680-
24
48
72
86 120
Time (Hours)
148
170
104
218
Figure 6.12. The effect of temperature on emission at 3% loading rate,
-------
300
M
VD
O
CD
200
e
Z
>
to
O
100-
104 218
Application
Figure 6.13. The effect of temperature on emission at 6% loading rate,
-------
600
U1
o
24
48
72
96
Tim* (Hour*)
140
Tilling
iTo il4 2~Te
Figure 6.14. The effect of temperature on emission at 10% loading rate.
208
-------
10
:
!
(Jl
Figure 6.15,
TOUI votalto IOM (kg)
Total 7-day loss as a function of variable temperatures
and loading rates.
-------
LH = 0%
RH= 76%
MC= 12%
8T = eO'F
Ul
ro
LR = 0%
RH = 62%
MC= 23%
3T = eO'F
Loading Rate
Relative Humidity
Soil Moisture Content
Soil Temperature
146
170
194
Application
96 120
Tim* (Hours)
Figure 6.16. The effect of increased relative humidity and moisture
content on emission.
-------
surface. Once this initial reservoir is depleted,
further loss depends on the rate at which additional
chemicals diffuse through the soil column to the surface.
Reduction of the humidity means that there is moisture
loss from the surface of soil column, and this results in
the movement of water to the surface of the soil column
which may enhance the rate of migration of the volatiles
to the surface; they are then lost by volatilization.
Under saturated conditions diffusion occurs at a slow
rate through the saturated soil column and under unsat-
urated conditions compounds volatilize from the soil-oil
surface and then diffuse as a gas through the soil atmo-
sphere.
The Effect of Soil Moisture Content on Emissions
All tests but one were run at 12 percent soil mois-
ture content. One test was made at approximately 23 per-
cent by weight soil moisture content. The loading rate
and soil moisture were 6 percent and 60°F, respectively.
As shown in Figure 6.16 and by the data in Table 6.24,
temperature appeared to have a pronounced effect on the
emission rate and mass loss. These data (Table 6.24)
suggest that as water content increased from 12 percent
to 23 percent, the mass loss over a seven day period in-
creased from 3.90 to 7.60 kg. The authors hypothesize
that this increase was due to water saturation of the
soil particle surfaces, thereby rendering the surfaces
unavailable for the compounds. The wetter soil surface
was much less permeable to the liquids in the sludge than
the dry surface.
THE EFFECT OF TILLING ON THE RATE OF EMISSIONS
In the field the plots were tilled to ensure aerobic
conditions for soil microorganisms and to enhan.ce the
biodegradation rate. To evaluate tilling effect on emis-
153
-------
sion in the laboratory, the soil and sludge mixture was
tilled two times, first on day three and then on day five
after application. It was found that tilling initially
increased the amount of volatilization for short periods
of time. Over a given time period, the emission rate was
higher when tilling occurred at the end of the time
period, than if frequent tilling occurred during the time
period. The concentration after tilling was observed to
be at least two times greater than before tilling. It
was also observed that the increase in volatilization due
to the first tilling was greater than that due to the
second and subsequent tillings. The effect of tilling
is illustrated clearly in Figures 6.4, 6.5, 6.9-6.12 and
6.16.
STATISTICAL ANALYSIS OF DATA AND DEVELOPMENT OF MODEL
Data was analyzed for the purpose of constructing a
'model'. This model was to relate emission rate mathe-
matically to variables such as soil temperature, soil
moisture content, relative humidity and sludge loading
rate.
The Statistical Analysis System (SAS) computer pack-
age was used to determine the significance of each
variable. Within that package multiple linear regression
model was used to process the data. By this procedure,
the parameters of the model were estimated on the basis
of least-squares regression. For any multiple linear
model, least-squares minimizes the residual sum of
squares and provides an unbiased, linear estimate with
minimum variance of parameters (Wallis, 1968).
After the model was constructed by estimating the
parameters of the regression line, the parameters were
tested to make sure that they were significantly differ-
ent from zero (Draper and Smith, 1976) . The t-test was
154
-------
used to determine the significance of each of the coef-
ficients. F-test was also used to determine the signif-
icance of the entire regression equation through the
analysis of variance.
.» a-
The backward elimination method and the coefficient
2
of multiple correlation (R ) were also used to select the
best set of independent variables in the model by utiliz-
ing the following variables: loading rate, soil tempera-
ture, soil moisture content, relative humidity and time
since application. In the backward elimination method
the deletion of an independent variable is based on the
result of an overall and partial F-test. The R value is
also calculated in each step and compared to each other.
Finally, residual analyses were performed to provide in-
formation as to whether or not the suggested model meets
the basic assumption of the regression technique (Draper
and Smith, 1976).
An attempt was made to analyze field data and devel-
op an appropriate model from these data. Nevertheless,
while several sets of regression trials were made, the
results were unacceptable. The effects of relative hum-
idity and soil moisture content could not be evaluated
and an appropriate model including all variables could
not be developed. Therefore, regression analysis was
made only on laboratory data (see Table B.2, Appendix B).
Besides the previously mentioned variables, an at-
tempt was made to include in the model such variables as
time since application, inverse of time (1/t) and several
combinations of these variables. However, only loading
rate, soil temperature, soil moisture content, relative
humidity and time since application were found to affect
significantly the emission rate. The others were
screened out by utilizing backward elimination method,
F-test and t-test.
155
-------
The form of equation used in this study is as follows;
Y = 6Q + B1X1 + 62X2 + 83X3 + 64X4 + 65X5 + e
where:
" Y = emission rate [g/hr],
6 = intercept of X on Y axis [g/hr],
X.. = percent loading rate [%] ,
X_ = soil temperature [°F],
X. = soil moisture content [%],
X. = relative humidity [%],
X5 = time since application
8- = (i=l-5) regression coefficients which weigh
the independent variables as their importance
[g/hr - % or g/hr - °F],
e = residual term [g/hr].
The model was first used in one step using the time
from starting of application until the end of the test.
The model found had an F-ratio of 17.51, and t-test
showed the coefficients of all independent variables
except relative humidity to be significantly different
from zero. Nevertheless, the coefficient of determina-
tion (R ) was only .44.
In an attempt to increase the value of the coeffi-
2
cient of determination (R ), including all five variables
in the model and fulfilling the basic assumption of the
regression analysis, analyses were made in two steps:
1. time <10 hours in which rapid decline of emis-
sion was observed.
2. time >10 hours in which slow decline of emis-
sion was noted.
After several trials utilizing the new approach, the
156
-------
following two models were found to be the best of sever-
al:
.Model I
Time <10 hours,
76.594 -I-
- 20.645
.830
Model II
Y = 76.594 -l- 9.985X1 + .769 X2 + 8.828 X3 - 2.025X4
- 20.645 X5
R2 = .830 F = 27.49
Time >10 hours,
.184 + .<
- .084 X,
= .184 + .931 XT + .268 X. + 1.879 X, - .371 X.
L 2 34
R2 = .766 F = 49.83
Table B.I, in Appendix B, presents the detailed informa-
tion for both models.
Both Models I and II are found to be significant
from a statistical standpoint. Coefficient of determina-
2
tion (R ) and F-ratios, are high and standard error of es-
timate in either model is low. Further, the signs of all
regression coefficients in both models are correct. Al-
so, the individual t-test for the regression coefficients
(Table B.I, Appendix B) show a high degree of signifi-
cance for the variables in the model. Negative signs for
time since application and relative humidity show that
these variables inversely affect the rate of emission of
volatiles.
To check the validity of the basic assumption of the
regression line, (linearity of the regression function,
the constancy of the error variance, and the independency
and normality of the error terms), residual analysis was
performed. This analysis did not show any reason to as-
sume that there was violation of the basic assumption.
Thus, these models were chosen for predictive purposes.
SIGNIFICANCE OF RESULTS FROM STANDPOINT OF AIR POLLUTION
The land treatment of petroleum sludge is a poten-
157
-------
tial source of air pollution. To check the significance,
the results are compared to National Air Quality Stan-
dards (CFR, Nov. 25, 1972). The primary and secondary
standards for hydrocarbon for a 3-hour average in time
was set 160 yg/m in 1971 which was changed to.240 pg/m
in 1979.
To obtain pollution concentration on the land treat-
ment area, the "box model" was used. In this model the
equilibrium concentration, C at a point a distance s
from the upwind edge of the land treatment area is:
e uz
where:
y = rate of emission per unit time per unit area
2
(g/hr/m ) determined from statistical models de-
veloped in this study
s = length of the box, lies in the direction of the
mean wind
u = average annual wind velocity in Oklahoma City
z = height of the box (average mixing height in
Oklahoma City)
Oil was applied to only one acre each day over a 10
day period before the sequence was repeated. For the
purpose of this study the following assumptions were
made:
V
A total land treatment area of 10 acres was assumed.
s = 4046.868 = 63.615 (area was assumed to be
square)
u = 6.69 meters/sec (13 mph) in Oklahoma City
z.. = 400 m, mean annual morning mixing height in
Oklahoma City
z_ = 1350 m, mean annual afternoon mixing height in
Oklahoma City
Furthermore, the following assumptions were made to
158
-------
determine the rate of emission from statistical models
developed in this study:
.soil moisture content = 15%
/! .soil temperature = 77°F
relative humidity = 65%
loading rate = 6%
time since application = 1.5 hours
volatility of sludge = 8.5%
Statistical Model I was used to calculate the emis-
sion rate from the last acre, 1.5 hours after applica-
tion, and Model II was used to determine the emission
rate from nine single previous applications for the other
nine acres. The equilibrium concentration was calculated
on the 10th day for each acre using the Box model. The
mean annual morning mixing height was used in this calcu-
lation. Table 6.25 presents the rate of emission and
equilibrium concentration of hydrocarbons after sludge
application from each single acre.
Assuming that pollutants were completely mixed over
a 4 hectare(10 acre) site, the equilibrium concentration
above the total land treatment area' was estimated 136
yg/m which is lower than Ambient Air Quality Standard
(240 yg/m ) . If all of the 10 acres are applied in one
day within 3-hours, the equilibrium concentration was
estimated 206.8 yg/m which is also below standard level.
Assuming loading rate of 10 percent, and all the
other conditions remaining the same, the equilibrium
concentration was estimated 166.72 yg/m which is again
below the standard level.
Therefore, based on the above information, properly
designed and managed land treatment systems of petroleum
sludge does not cause air pollution problems. If the
process is operated properly, there is no need for a
buffer zone unless the sludge is highly volatile (>14%) ,
159
-------
:TABLE 6.25
RATE OF EMISSION AND EQUILIBRIUM
CONCENTRATION OF HYDROCARBONS AFTER
SLUDGE APPLICATION
Days
After
Application
.0625 = 1.5 hr
1
2
3
4
5
6
7
8
9
Acre
No.
10
9
8
7
6
5
4
3
2
1
Y = Pate of
Emission
Ig/hr/m2)
9.90
1.69
1.57
1.45
1.32
1.21
1.09
.97
.85
.72
Total
C =
e
Equilibrium
Concentration
(wg/m3)
65.39
11.10
10.32
9.50
8.70
7.90
7.20
6.40
5.60
4.70
136.81
160
-------
temperature and soil moisture content are high or loading
rate is greater than 10 percent. Under these conditions
it i^ preferable to apply (against the wind-ward direc-
tion.)..in the afternoon when mixing height is higher than
.*
in the morning.
ANALYSIS OF GAS CHROMATOGRAPHIC DATA
As previously discussed in Section 5, the air sam-
ples collected over sludge-laden plots were analyzed by
gas chromatography (GO using a flame ionization detec-
tor. Because of GC malfunctioning while conducting field
studies, most of the samples collected from the field
plots and some of the data were discarded. However, lat-
er, after the GC problems were resolved, many samples
were taken from laboratory experiments and analyzed at
appropriate times.
Of the volatile hydrocarbons identified, only four-
teen were quantified. These target compounds along with
their vapor pressures at 35°F, 60°F and 85°F and their
boiling points are presented in Table 6.26 according to
increasing boiling points or decreasing vapor pressures.
Besides these compounds, other compounds such as propa-
nol, 2-propanone, 2-butanone, 2-pentanone, cyclohexanol,
ethylcyclopentane, 2-methyl-l-pentanol and 1,1-Dimethyl-
cyclopentane, were identified by GC-MS in the RSKERL
laboratory in Ada, Oklahoma.
Tables B.I through B.9 in Appendix B summarize data
on all of the pollutants measured during the nine labo-
ratory studies. The data in these tables are grouped ac-
cording to three different temperatures and three differ-
ent loading rates. In addition, Table B.14 presents data
from field experiments.
Much of the information in Tables B.4 through B.14
is self-explanatory, so only salient observations will be
161
-------
TABLE 6.26. BOILING POINTS AND VAPOR PRESSURES
OF MEASURED COMPOUNDS
Compound Name
Pentane
Cyclopentane
Hexane
Methylcyclopentane
Benzene
2 ,4-Dimethylpentane
Cyclohexane
3-Methylhexane
Methylcyclohexane
2 , 5-Dimethylhexane
2 ,3 ,4-Trimethylpentane
3-Methylheptane
2 ,2 ,5-Trimethylhexane
1 ,4-Dimethylbenzene
Boiling
Point °F
36.1
49.2
69
72
80.1
80.5
80.7
91.85
100.9
109
113.467
118.925
124.084
138.351
Vapor Pressure
mm/Hg
35°F
199.52
112.20
47.32
47.32
28.11
31.62
26.61
17.78
12.59
6.68
6.68
4.47
4.47
1.496
60°F
334.96
199.53
94.41
94.41
63.10
63.10
53.09
35.48
26.61
14.96
14.96
10.59
10.00
3.98
85°F
562.34
398.10
177.82
177.82
117.48
117.48
112.20
70.79
50.11
31.62
31.62
23.71
19.95
10.00
162
-------
made here.
The above mentioned tables provide information on
emission rates at different times since sludge applica-
tion;, .at three temperatures, at three loading rates and
due to tilling. Included in the tables are total emis-
sion rates of the fourteen compounds at each time with
the corresponding total volatile emission rates measured
as hexane. In addition, the percentage ratio of the
fourteen hydrocarbons from GC analyses to the total
volatile hydrocarbons measured at the same time with TLV
Sniffer is presented.
Figure 6.17 shows the time relationship between
emission and loading rate at 85°F for benzene, and Figure
6.18 demonstrates the relationship of emission rates and
temperature at 10% loading rate for benzene. Also Fig-
ures B.I through B.16 in Appendix B illustrate the time-
concentration curves for other compounds.
It is clear from these figures that the rate of
emission of each hydrocarbon increased with increasing
temperature and loading rate. For exact emission rates
see Tables B.4 through B.13 in Appendix B.
Tables B.4 through B.14 in Appendix B show that com-
pounds having low boiling points and high vapor pres-
sures, such as pentane, cyclopentane, methylcyclopentane
and hexane, had lower, emission rates than high boiling
point and low vapor pressure compounds. This may pos-
sibly be related to the fact that high vapor pressure
hydrocarbons have already been vaporized during transpor-
tation and storage of sludge.
The higher emission rates were found among the
hydrocarbons with boiling point ranges from 70 to 119°C.
Among these hydrocarbons 2,3,4-Trimethylpentane, with a
boiling point of 113.467°C, had the highest rate. The
next highest rates pertained to 2,4-Dimethylpentane and
163
-------
3.9H
2.74
E 3.
M -
1 J
5 2.I4-:
5 i
N 2.H
R
R
T 1.6
E
N 1.5-
O.Q-i
vfiPCR
o 35 r ; =3.!? e 63 " : :'."'.-5 «
BOILING POINT-eO. i
TEMP-85
20 40 60 80 100 120 1HQ 150 250 2C-C'
HOURS SINCE RPPLICBTION
LEGEND-: LOflORRTE *-^. 3 i . 6 »-. JQ
Figure 6.17. Time relation of emission rate
and loading rate-Benzene.
Reproduced from
best available copyA
164
-------
3.-9-1
3.5-
3.3-3
3.0
1.8-1
1.5
1
j.
l
ii
VRPOR PRESSURES
2S.:: e 35 F : 63.10 e £0 f -. I17.4? e 55
BOILING POINT.80.1
LOPDRRTE-1C
1
0.34
0 20 40 63 8C 100 120 mC 160 !SC SCO
HOURS SINCE RPPLICRTJON
LEGEND: TEMP «-^-^. 35 « « « 6C »-.-^ 85
Figure 6.18. Time relation of emission rate
and temperature-Benzene.
165
-------
3-Methylheptane, respectively.
It was observed that the emission rates of all
hydrocarbons decreased with time (Figures 6.17 and 6.18).
In some cases, the opposite trends were seen (cyclopen-
tane and pentane); the emission rate was low immediately
after application, and it increased for 10 to 60 minutes,
and decreased, thereafter, and then followed the pattern
of other compounds.
It was further found that, in general, the hydro-
carbons identified immediately after sludge application
were also identified several months later, but their
relative emission rates were much lower.
It is clear from Tables B.I through B.9 and corre-
sponding figures that tilling increased the release rate
of each compound. Figures 6.19 and 6.20 show before- and
after-tilling concentrations of each compound. Air sam-
ples which produced these chromatograms were taken from
plot 4 en April 1983, which had received sludge on Novem-
ber 17, 1982.
FATE OF PRIORITY POLLUTANTS
The fate of priority pollutants present in oily
sludge disposed of on land has not been extensively stud-
ied. Therefore, one of the objectives of this study was
to determine the movement, loss, and degradation of the
priority pollutants identified in the applied residues.
The zone of incorporation, (the unsaturated zone below
this zone) was analyzed for priority pollutants. The re-
sults are presented in this section.
The priority pollutants found in the sludge applied
(Batches I and II) are presented in Tables 6.27 and 6.28
and the results of the monitoring priority pollutants are
presented in Tables 6.29 and 6.30.
From the analysis of these results several observa-
166
-------
:>.)
IS.J1
tuiylmw calortd* (III
at.I* cycloiwmw
JI. It MUiyl
2«.4J
11.2} I.4-01M
TT.41
\ 4«. I
42. 4(
«4.JJ
1 AVI «»* t'.'M
Figure 6.19. Chromatogram of air sample taken
from plot 4 (before tilling).
167
Reproduced from
best available copy.
-------
*rtr-
f '*"
Mtnyl«n«
ere
> :..«
> it. 4* mt«M
^ i«- « cyelokuam
^^ n. 4r i-
-------
TABLE 6.27. PRIORITY POLLUTANTS PRESENT IN THE OILY
RESIDUES, BATCH I
Nam.es of Compounds
Range of Cone, in ppb
Napthalene
N-nitrosodiphenylamine
Isophorone
Fluorene
Phenanthrene
Anthracene
Pyrene
Chrysene
Benzo(A)anthracene
2,4-Dinitrotoluene
Trichloroethylene
Benzene
Ethylbenzene
1.61 - 136.61
3.4 x 10~4 - 0.075
T - 39.76
T - 1.64
2.83 x 10~3 - 0.896
1.13 x 10~4 - 0.574
4.04 x 10~5 - 0.056
T
T
0.087 - 630.66
0.047 - 137.70
T - 16.83
7.51 - 90.9
Note: T denotes trace amounts less than 10
-5
ppb.
TABLE 6.28. PRIORITY POLLUTANTS PRESENT IN THE OILY
RESIDUES, BATCH II
Compound Present
Cone, in ppb
Toluene
Ethylbenzene
Isophorone
3.5330
0.3740
0.0004
169
-------
TABLE 6.29. PRIORITY POLLUTANTS PRESENT AT DIFFERENT
TIMES FOR PLOT NO. 30
" ' Concentration Range in ppb
Compounds 4/7/82 9/10/82 9/26/82 11/8/82 12/20/82-
6/9/83
Set I Set II Set III Set IV Set V - VI
Isophorone 10.74-68.0 0.064-1.299
Fluorene 10.21-30.35
Phenan-
threne
Anthracene
Trichloro-
ethylene
Benzene
0.088-126.4
0.002-0.021
1.98-2.67 - 0.514-0.762
T - 0.0011 T - 0.0037
None
Present
0.0010
Ethylbenzene T - 0.0017
Nitrobenzene - 0.019-0.038
Phenol
2-Nitrophenol
Pentachloro-
phenol
Pyrene
T - 0.00019
T
0.0007
-5
Note: T denotes trace amounts less than 10 ppb
170.
-------
TABLE 6.30,
Benzene
Phenol
Pyrene
PRIORITY POLLUTANTS PRESENT AT DIFFERENT
TIMES FOR PLOT NO. 35
Compounds
Isophorone
Phenanthrene
Anthracene
Fluorar.thene
2,4-Dinitro-
toluene
6/7/82
Set I
0.728-14.7
0.004-522,98
0.002-0.267
0.006-0.065
0.41-3.62
Concentration Range in ppb
9/10/82 9/26/82 11/8/82 -
6/9/83
Set II Set III Set IV - V
T
-
None
Present
1.572
0.0002-0.0004
0.0001-.0009
0.0001-0.0002
Note: T indicates trace amounts less than 10 ppb
171
-------
tions have been made:
1) The initial concentrations of organic compounds
were in the ppb range.
'.i 2) The concentrations of the compounds decreased
with time.
3) The number of compounds decreased with time.
4) The 2nd batch of oily residue obtained did not
have as many pollutants as the 1st batch.
5) After a period of 426 days the priority pollu-
tant concentrations were below the detection
limit of the extraction and analytical proce-
dures.
6) Initially there were no phenolic compounds pre-
sent in the sludges, but after a period of 387
days there were phenolics present. This leads
to the conclusion that they were formed in the
soil matrix.
On combining the results of the zone of incorpora-
tion and the unsaturated zone monitoring, it can be said
that there were no contamination problems in terms of
priority pollutants. It appears that, since the concen-
tration of the compounds were very low in the sludges and
also there were no compounds present in the unsaturated
zones the most probable 'fate' of these compounds was
volatilization or degradation.
UNSATURATED ZONE MONITORING
The results of the unsaturated zone monitoring on
plots 30 and 35 for priority pollutants are presented in
Table 6.31. It can be seen from the data that not as
many compounds were identified in the site soil as were
present in the sludge, and that over a 15 month period,
the concentration of priority pollutants decreased below
the detection limits of the extraction and analytical
172
-------
TABLE .6,31. ORGANIC PRIORITY POLLUTANTS FOUND
IN THE UNSATURATED ZONE
Plot No. /Date
of Sampling
30,
4/7/82
35,
4/7/82
Compounds
Present
'Chloroform
Trichloroethylene
'Chloroform
Trichloroethylene
Benzene
Isophorone
Phenanthrene
Anthracene
Fluoranthene
Range
in ppb
T -
T -
T -
T - .
T -
T -
T -
T
of Cone.
12.09
3.48
103.01
98.97
1.85xlOJ
0.026
30, 'Chloroform 26.29 - 65.69
9/30/82 Trichloroethylene T - 11.02
Benzene . T
35, 'Chloroform 0.552 - 57.34
9/30/82 Trichloroethylene T - 1.853
30, 35 None
7/15/83 present
Note: T indicates trace amounts less than 0.1 ppb
* Chloroform appears to be a contaminant, since it was
also present in the blanks.
173
-------
procedures. These results indicate that no significant
movement of priority pollutants into the soil of the un-
saturated zone, below the zone of incorporation (30 cm),
(1^.3,,in) occurred over the 15 month period.
FATE OF METALS IN SOIL
As a part of the evaluation of land treatment, the
concentration of metals in the soil was monitored period-
ically. The concentration of selected metals in the site
soil before application of any residues was determined
and compared to the concentration of the same metals in
the soil at different times during the project.
Table 6.32 lists the concentration of metals in the
site soil before application of residues. The values
listed are means from at least 21 different samples an-
alyzed from the site. Table 6.33 lists the metal concen-
trations in the applied oil. Tables 6.34 through 6.37
list metals concentrations in different plots, showing
how the concentrations varied over time.
As can be seen from Table 6.32, the background soil
contained low metal concentrations. The applied sludge
also contained low metal concentrations, as shown in Ta-
ble 6.33.
No definite trends in metal concentration buildup
could be identified for the metals except for Cr and Zn.
Chromium and zinc did show an increase in concentration
in the soil which was significant at a = 0.05. This in-
crease occurred in all plots. No significant increase in
the concentration of Cu, Ni, Pb or Cd occurred between
8/21/81 and 6/9/83, the first date of application and the
final analysis date, respectively.
The theoretical amount of the metals which should be
present in the soil was determined by calculating the
amount of metal applied in the sludge, and adding the
174
-------
TABLE 6.32. BACKGROUND METAL CONCENTRATIONS IN SITE SOIL
- -"' Element
Cu
Cr
Zn
Ni
Pb
Cd
*
Cone, (mg/kg)
10.1
12.2
29.7
22.0
14.7
<0.5
Mean of at least 21 values.
TABLE 6.33. METALS IN APPLIED OIL (mg/kg)
Batch No.
1
2
3
4
Zn
12.97
25.49
349.42
210.26
Ni
22.20
12.57
10.96
9.32
Cu
1.00
0.47
6.69
7.21
Pb
2.00
1.12
22.31
10.41
Cr
<0.2
1.65
23.24
12.53
Cd
0.25
<0.50
16.04
10.32
175
-------
TABLE 6.34.CONC. OF METALS IN PLOT 8
Metal
Cu
Cr
Zn
Ni
Pb
Cd
Metal
Cu
Cr
Zn
Ni
Pb
Cd
Bkg.
10.1
12.2
29.7
22.0
14.7
<0.5
TABLE 6.35.
Bkg.
10.1
12.2
29.7
22.0
14.7
<0.5
Cone, (mg/kg)
11/17/82 6/9/83
23.5 9.8
24.0 23.3
35.0 83.3
20.0 15.9
24.0 14.3
2.0
CONC. OF METALS IN PLOT 13
Cone, (mg/kg)
11/17/82 12/20/82 6/9/83
22.0 18.0 10.1
17.7 22.0 26.6
33.7 53.0 48.3
16.3 15.0 12.3
16.0 17.0 17.0
<0.5 <0.5 1.0
176
-------
TABLE 6.36. CONC. OF METALS IN PLOT 20
Metal
Cu
Cr
Zn
Ni
Pb
Cd
Bkg.
10.1
12.2
29.7
22.0
14.7
<0.5
Cone, (mg/kg)
11/17/82
59.0
15.7
38.7
15.7
16.0
<0.5
6/9/83
13.9
25.6
45.7
15.7
12.7
<0.5
TABLE 6.37. CONC. OF METALS IN PLOT 26
Metal
Cu
Cr
Zn
Ni
Pb
Cd
Bkg
10.
12.
29.
22.
14.
<0.
1
2
7
0
7
5
11/17
22.
22.
14.
14.
14.
<0.
/82
5
0
5
5
0
5
Cone, (mg/kg)
12/20/82
22
18
-
16
19
1
.5
.0
.5
.0
.3
6/9/
9.
23.
49.
18.
13.
0.
83
7
7
7
0
0
5
177
-------
background concentration of the metal present in the soil
to this value. These theoretical concentrations were
then- compared to the values obtained by analyzing the
site::.soil at the end of the project. There was a
reasonably good agreement between the two sets of values,
except for chromium, where the theoretical values were
appreciably lower than the measured values. The data for
this comparison is presented in Table 6.38.
No significant buildup of metals occurred during the
project period. Zinc and chromium were present at levels
significantly above background, but the absolute values
were still very low. Table 6.40 shows accepted metal
concentrations which can be tolerated in the soil as a
result of irrigation or other activities. If the metal
concentrations in the plot with the highest loading rate
are considered - 27 percent over 22 months - the useful
life of the plot would be limited by the zinc and cadmium
concentrations. Using the values 'in Table 6.40, the
cadmium concentration in the soil would reach the
critical level in 24 years, and the zinc concentration in
17 years. Thus, if sludges with the concentrations of
metals given in Table 6.33 were applied, the life expec-
tancy of the site would be 17 years.
Soil samples from below the zone of incorporation
were also analyzed for metals, to determine if any
migration of metals had taken place. There was no
significant increase in the metal concentration below the
zone of incorporation. Table 6.39 shows the results of
deep core analysis. Raw metal data is presented in
Appendix C.
MODELING AND DESIGN OF LAND TREATMENT SYSTEMS
Several recommendations relevant to process modeling
178
-------
TABLE 6.38. COMPARISONS OF METAL CONC,
WITH AMOUNT APPLIED
PRESENT IN SOIL
Plot
No.
Zinc
Bkg.
13
21
8
20
26
Nickel
Bkg.
13
21
8
20
26
Copper
Bkg.
13
21
8
20
26
Lead
Bkg.
13
21
8
20
26
Total Oil
Applied (1)
(%)
-
9.2
22.4
26.8
14.3
12.0
^
9.2
22.4
26.8
14.3
12.0
-
9.2
22.4
26.8
14.3
12.0
-
9.2
22.4
26.8
14.3
12.0
Metal Cone.
Applied (2)
(mg/kg)
44.28
70.51
72.36 '
46.60
46.67
^
25.04
70.51
29.04
26.26
25.77
-
12.27
12.80
12.88
12.29
12.37
-
15.22
17.13
17.31
15.54
15.44
Metal Cone.
Present (3)
(rag/kg)
35.15
48.25
69.00
83.25
45.70
37.00
22.92
12.25
69.00
15.00
15.70
14.50
12.00
10.13
9.67
9.75
13.90
13.00
14.66
17.00
16.67
14.25
12.70
14.00
(continued)
179
-------
TABLE 6.38. (continued)
Plot
Total Oil
Applied(1)
Metal Cone,
Applied(2)
(mg/kg)
Metal Cone,
Present(3)
(mg/kg)
Chromium
Bkg.
13
21
8
20
26
Cadmium
9.2
22.4
26.8
14.3
12.0
14.
15,
15,
17,
13
80
88
26
14.25
13.60
26.23
25.67
23.25
25.60
22.00
Bkg.
13
21
8
20
26
9.2
22.4
26.8
14.3
12.0
_
0.74
1.93
2.00
0.79
0.84 '
<0.50
1.00
1.83
2.00
<0.50
<0.50
(1) Total oil applied to plot during the project on a
dry weight basis.
(2) Theoretical cone, of metal in soil .based on amount
applied plus background.
(3) Cone, of metals in soil at end of project by
analysis.
180
-------
TABLE 6.39. METAL CONCENTRATION IN DEEP CORES (mg/kg)
Metal
Cd
Cr
Cu
Ni
Pb
Zn
Cu
Ni
Zn
Pb
Cd
Cr
Depth
91 -
152 -
91 -
152 -
91 -
152 -
91 -
152 -
91 -
152 -
91 -
152 -
0 -
30 -
61 -
0 -
30 -
61 -
0 -
30 -
61 -
0 -
30 -
61 -
0 -
30 -
61 -
0 -
30 -
61 -
(cm)
107
168
107
168
107
168
107
168
107
168
107
168
30
61
91
30
61
91
30
61
91
30
61
91
30
61
91
30
61
91
Plot
#30/16.1
<.50
.50
29.50
36.00
17.00
16.00
29.00
36.50
22.50
28.50
40.50
37.50
5.5
11.8
32.0
12.0
21.8
28.0
35.5
41.0
52.0
7.0
7.0
11.0
0.5
0.5
0.5
15.5
24.8
32.5
No./% Oil
#35/17.
<.50
.50
31.00
29.00
15.00
25.00
24.00
34.00
14.00
21.50
42.50
43.00
9.5
14.0
14.0
10.5
16.5
19.0
46.0
49.5
52.0
19.0
13.0
15.0
<0.5
0.5
0.5
30.0
35.5
34.0
Applied
7 #21/22.4
<.50
.50
28.00
34.83
14.00
23.60
23.25
31.80
21.63
18.40
37.38
42.70
9.0
9.0
11.5
12.5
10.0
15.5
47.3
40.0
43.0
12.5
18.0
17.5
0.5
<0.5
0.5
22.0
32.0
30.5
181
-------
TABLE 6 ..40. ACCEPTED METAL CONCENTRATIONS IN SOIL AS
A RESULT OF IRRIGATION OR OTHER ACTIVITIES
Element Concentration (mg/kg)
As 500
Cd 20
Co 500
Cr 1,000
Cu 250
Ni 100
Pb 1,000
Zn 500
Brown (1980)
182
-------
and design were made based on data presented in the pre-
ceding subsections. Although overall oil losses increase
with .-increasing loading rates and decreasing loading fre-
que.nci.es, there is a practical limit above which opera-
tional consideration such as ability to operate cultiva-
tion equipment and control runoff became limiting fac-
tors.
A maximum hydraulic loading for this research site
based on existing field conditions was found to be ap-
proximately 40 1/m (1 gal/ft ) . At the oil concentra-
tions of the sludges used in this study (60 - 90 percent)
the maximum hydraulic loading corresponds to approximate-
ly 7 percent dwb in terms of the increase in oil concen- -
tration in a 30 cm depth zone of incorporation. Though
higher loadings were in fact made, operational problems
such as those described above inevitably resulted.
It must be noted that the duration of the study pe-
riod was not long enough for the systems to approach
equilibrium. Therefore, the maximum hydraulic loading of
40 1/m per application will probably not be attainable
when the system reaches equilibrium. Depending upon the
final equilibrium concentration and the oil concentration
of the sludge a hydraulic loading to achieve an oil con-
tent per application of 3 - 4 percent dwb is an achiev-
able goal. Except for very low sludge oil concentrations
in which the long-term hydraulic loading (and not the
single application) becomes the limiting constraint,
annual oil loading rate could be maintained for low oil
content sludges by increasing the number of applications.
It is suggested that, from a practical standpoint,
physical site conditions are the primary determinative
controlling loading rates and, therefore, loss rates in
an oily waste land treatment system. Therefore, the
authors predict that in any properly operated system,
183
-------
treating API Separator sludges from petroleum refineries
loss rates equivalent to those found in this study would
be ejcpected.
i JOily waste land treatment systems should be designed
for 'equilibrium conditions'. For the purpose of this
discussion, equilibrium is reached when the amount of
degradable material applied is removed (via degradation
and volatilization) in the period prior to the next ap-
plication. This definition is somewhat oversimplified,
since the concentrations and loss rates for degradable
waste fractions are in reality dynamic due to a combina-
tion of factors. Therefore, 'equilibrium1 applies to
time intervals over which sufficient loading/loss cycles
have occurred such that process fluctuations are insig-
nificant. This approach ignores the possible buildup of
refractory organics and inorganics which may be produced
in the process or be present in the waste sludge. Cer-
tainly these are important considerations. The build up
of refractory compounds was not found to be a significant
problem in this study, however, equilibrium conditions
were not achieved.
Though it was shown that the various oily fractions
are removed from the zone of incorporation at different
rates, the metabolic pathways and biochemical interrela-
tionships are not sufficiently understood to warrant the
use of a multiple-substrate process model. Thus, a pseu-
do single-substrate model was developed. Continuing mon-
itoring would support or reject the validity of this sim-
plifying assumption. The use of a single substrate model
had distinct advantages. Measurement of the major pro-
cess control parameter, substrate concentration, is made
easier if fractionation of the recovered oil is not re-
quired.
Determination of a composite overall rate coeffi-
184
-------
cient also makes the design methodology more applicable
to a variety of oily substrates. It is recognized that
the ..coefficient is not constant but a function of many
factpr.s. However, in the design methodology discussed
below the coefficient has been assumed constant. The re-
sults of these investigations of oil loss kinetics indi-
cate that a first-order biodegradation rate constant of
0.003 day is reasonable for the API Separator sludge
used in this study. Based on the first-order reaction
kinetics a simplified process model was developed. The
following general assumptions apply:
1) Single component substrate (oil) .
2) Constant first-order rate coefficient.
3) Application rate and frequency held constant.
If, at equilibrium, the amount of substrate added, L , is
a
equal to the amount degraded, (L - L. ) , then the follow-
ing first-order relationships are valid:
T - T o~Kt
Lt - Lo e
L = L - L.
a o t
- L - L e~Kt
- Lo Lo e
eKt)
And therefore,
L
L - a
0 (1 - e-Kt)
is an expression for the maximum equilibrium concentra-
tion, where 't1 is the (constant) time between applica-
tions of L . With L known, the number of cycles 'n1
a o
required to reach equilibrium may be found from the
equation:
T - T r »
L = L I e
0 a i-o
185
-------
If equilibrium is arbitrarily defined as having been
reached when L of the 'nth1 cycle is within some per-
centage of the theoretical maximum L , then the above
equation may be easily solved for 'n1 by iteration.
Table 6.41 presents a matrix of equilibrium values
for combinations of loading rate and loading frequency
(LR/LF) which bracket anticipated practical loading pos-
sibilities. A value of first-order rate coefficient of
0.003 day was used in the calculations. Equilibrium
was reached when an increase in maximum concentration was
less than 1 percent of the previous maximum. If a con-
stant loading rate and loading frequency were used the
system would require four to five years to reach equilib-
rium.
In addition to the maximum and minimum equilibrium
concentrations and the number of cycles required to reach
equilibrium, the time required after cessation of appli-
cations to reduce the substrate concentration to 2 per-
cent dwb was computed. The value of 2 percent oil in
soil was arbitrarily selected as a milestone correspond-
ing to site closure, and cessation of active land treat-
ment operations. During the subsequent post-closure
period the soil could be revegetated if the oil concen-
tration was less than 2 percent and toxics are not pres-
ent above the inhibition concentration.
As expected, the higher loading rates required some-
what longer periods to reach equilibrium, with the higher
ultimate equilibrium concentrations than lower loading
rates. Increasing loading frequency reduced the time to
equilibrium and the maximum concentrations, but raised
the minimum equilibrium concentrations.
In order to evaluate the relative effects of changes
in rate coefficients on equilibrium concentrations,
values of 0.001 day and 0.005 day were applied to the
186
-------
TABLE 6.41. EQUILIBRIUM VALUES ASSUMING K = .003 DAY*1
: iR/LF
(% dwb) / (year"1
12/1
12/2
12/4
12/6
12/12
9/1
9/2
9/4
9/6
6/1
6/1
6/4
6/6
La
) (% dwb)
12
6
3
2
1
9
4.5
2.25
1.5
6
3
1.5
1
e'Kt
.334
.578
.761
.833
.913
.334
.578
.761
.833
.334
.578
.761
.833
L max
o
(dwb)
18.02
14.22
12.55
11.98
11.49
13.51
10.66
9.41
8.98
9.01
7.11
6.27
5.00
Lt eq
(% dwb)
6.02
8.2.2
9.55
9.98
10.49
4.51
6.16
7.16
7.48
3.01
4.11
4.77
4.99
n
5
9
17
25
47
4
8
16
24
4
8
15
23
(days)
730
650
610
600
580
640
560
520
500
500
420
380
370
187
-------
TABLES.42. EQUILIBRIUM VALUES ASSUMING OTHER
RATE COEFFICIENTS
LR/LF L
{% dwb) /(year"1) (% dwb)
K = .005 days"1
9/1 9
9/2 4.5
9/4 -2.25
9/6 1.5
K = .001 Days"
9/1 9
9/2 4.5
9/4 2.25
9/6 1.5
-Kt
e
.161
.402
.634
.738
.694
.833
.912
.941
L max
o
(dwb)
10.73
7.53
6.15
5.73
29.41
26.94
25.57
25.42
Lt eq
(% dwb)
1.73
3.03
3.90
4.23
20.41
22.44
23 ."32
23.92
n
3
5
9
15
12
24
47
70
t2%
(days)
340
270
230
210
2690
2600
2550
2540
188
-------
annual loading rate of 9 percent (Table 6.42). Dramatic
increases in both equilibrium concentration and time re-
quired to reach equilibrium and degrade to values for
pos.t
-------
Advantages to the slow start-up approach would be
greatest for those refineries which have existing sludge
treatment and/or disposal systems. Redirection of an ex-
isting steady state waste stream to a land treatment site
'". =
is essentially all that would be required for conversion
to the system. Low initial sludge loadings would also
build in a certain factor of safety, in that early moni-
toring of the system would allow changes in the design
loading rates prior to a build-up to unacceptably high
levels. Determination and refinement of the biokinetic
constants would also be possible with the slow start-up
approach. The potential for build-up of refractory or-
ganics and inorganics could be assessed prior to reaching
unacceptably high concentrations, and the planned design
life of the systems modified accordingly.
It is highly recommended that initial soil testing
and pilot studies be conducted prior to design and con-
struction of an oily waste land treatment system. Test-
ing the mechanical characteristics of potential site
soils both before and after oily sludge addition in the
laboratory is critical in order to estimate important
characteristics of the soil during system operation.
190
-------
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196
-------
APPENDIX A
OIL LOADING AND CONTENT DATA
197
-------
TABLE A.I. OIL LOADING DATA
Plot
1
2
4
5
Date
82181
11982
71982
81782
90982
100482
101482
110282
111782
82181
11962
30882
71382
81782
92382
92382
101482
101482
111782
122082
82181
12082
71382
81282
92382
101282
110282
111782
82181
12082
71382
81282
92382
101282
110282
111782
Elapsed Time
0
151
332
361
384
409
419
438
453
0
151
199
326
361
398
398
419
419
453
486
0
152
326
356
398
417
438
453
0
152
326
356
398
417
438
453
Percent Applied*
1.25
2.50
2.93
2.93
2.93
2.50
2.50
2.50
0.83
1.25
1.25
1.25
1.25
0.29
-
2.20
-
1.25
1.25
0.29
0.58
0.58
0.58
0.58
0.41
0.58
0.58
0.86
1.92
1.92
1.92
1.92
1.92
2.50
1.92
(continued)
. 19C
-------
TABLE A.I. (continued)
Plot
6
7
8
9
10
11
Date
82181
11982
41582
71982
81782
91082
101482
111782
82181
11982
42082
72082
81782
92382
92382
101282
111782
82181
11982
111782
82181
12082
30882
71382
81282
92382
110282
111782
122082
82181
12082
72082
110982
82181
11982
71982
81782
91082
101282
110282
111782
Elapsed Time
0
151
237
332
361
385
419
453
0
151
252
333
361
398
398
417
453
0
151
453
0
152
199
326
356
398
438
453
486
0
152
333
445
0
151
332
361
385
417
434
453
Percent Applied*
1.25
2.50
2.50
2.93
2.93
2.93
2.50
2.50
0.48
1.15
1.15
1.15
1.15
1.15
-
1.15
1.15
7.48
11.55
7.75
0.32
0.58
0.58
0.58
0.58
0.58
0.58
0.58
0.58
0.96
3.45
3.45
6.90
0.48
1.15
1.15
1.15
1.15
1.15
1.15
1.15
(continued)
199
-------
TABLE A.I. (continued)
Plot
13
i -." '' '
14
15
16
17
18
Date
82181
12082
30882
42082
72082
81282
92382
92382
101282
111782
122082
82182
12082
71382
81282
92382
101282
110282
111782
82181
12082
71382
110982
82181
11982
111782
82181
11982
111782
82181
11982
30992
71382
81282
92382
101282
110282
111782
122082
Elapsed Time
0
152
199
252
333
356
398
398
417
453
486
0
152
332
356
398
417
438
453
0
152
332
445
0
151
453
0
151
453
0
151
199
326
356
398
417
438
453
486
Percent Applied*
0.58
0.96
0.96
0.96
0.96
0.96
0.96
-
0.96
0.96
0.96
0.29
0.58
0.58
0.58
0.58
0.58
0.58
0.58
0.96
3.45
3.45
6.90
3.90
3.00
3.45
3.45
3.45
1.73
0.19
0.29
0.29
0.29
0.29
0.29
0.29
0.29
0.29
0.29
200
-------
TABLE A.I. (continued)
Plot
20 :
T » " *
21
22
23
24
25
26
Date
82181
10282
41582
72082
81282
92382
101282
111782
82181
11982
111782
82181
11982
111782
82181
12082
72082
122082
82181
12082
71382
110982
82181
12082
30882
41582
72082
81282
92382
101282
82181
11982
30882
42282
71982
81782
91082
101282
111782
122082
Elapsed Time
0
152
247
333
356
398
417
453
0
151
453
0
151
453
0
152
333
486
0
152
332
445
0
152
199
247
333
356
398
417
0
151
199
254
332
361
385
417
453
486
Percent Applied*
0.86
1.92
1.92
1.92
1.92
1.92
1.92
1.92
7.48
7.42
7.48
5.18
11.50
5.75
2.49
7.48
7.48
4.23
0.58
1.73
1.73
3.45
0.20
0.29
0.29
0.29
0.29
0.29
0.29
0.29
0.83
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
(continued)
201
-------
TABLE A.I. (continued)
Plot
28
i -" ' '
29
30
31
32
34
35
Date
82181
12082
72082
110982
82181
12082
72082
110982
82181
12082
122082
82181
11982
111782
82181
11982
30882
42082
81782
92382
92382
101482
111782
122082
82181
11982
30882
41582
71382
81282
92382
101482
122082
82181
12082
122082
Elapsed Time
0
152
333
445
0
152
333
445
0
152
486
0
151
453
0
151
199
252
361
398
398
419
453
486
0
151
199
237
326
356
398
419
486
0
152
486
Percent Applied*
1.73
5.75
5.75
11.50
1.73
3.52
5.75
11.50
5.75
6.90
3.45
3.45
3.45
1.73
0.32
0.58
0.58
0.58
0.58
0.58
-
0.58
0.58
0.58
0.58
0.96
0.96
0.96
0.96
0.96
0.96
0.96
0.96
5.18
6.81
5.75
(continued)
202
-------
TABLE A.I. (continued)
Plot
36 .'.
s -
38
Date
82181
11982
71982
122082
82181
12082
71382
110982
Elapsed Time
0
151
332
486
0
152
326
445
Percent Applied*
2.49
6.09
4.04
3.97
0.58
1.73
1.73
3.45
* in % dry weight basis
203
-------
TABLE A.2. SOIL SOIL CONTENT DATA
Plot Oil Content
1 r . 9.47
11.16
11.83
12.92
12.00
12.58
12.26
12.48
11.96
9.55
8.71
9.69
7.81
8.07
7.49
8.71
7.81
4.91
6.06
7.93
5.50
4.53
5.08
4.05
4.86
2 6.15
6.97
7.17
5.09
5.07
4.96
5.38
4.96
4.60
5.94
6.39
2.94
3.63
3.51
3.78
4.29
3.62
3.99
Date
60983
60983
60983
111782
111782
111782
101482
101482
101482
100482
100482
100482
90982
90982
90982
81782
81782
81782
81782
81782
81082
81082
81082
81082
81082
60983
60983
60983
122082
122082
111782
111782
111782
101482
101482
101482
100782
100782
100782
92382
92382
92382
92282
(continued)
204
-------
TABLE A.2. (continued)
Plot Oil Content
2 (eon't) 4.15
* -": 3.37
3.78
3.78
4.41
2.27
3.28
3.87
3.28
3.54
1.75
2.15
2.23
1.59
2.60
3 0.20
C.18
0.56
0.17
0.26
0.10
4 1.84
1.61
1.42
1.54
1.74
1.59
2.33
2.21
2.21
1.62
1.90
1.71
1.33
1.30
1.30
1.04
0.96
0.94
1.10
1.08
Date
92282
92282
90982
90982
90982
81782
81782
81782
81782
81782
81082
81082
81082
81082
81082
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
51083
51083
51083
111782
111782
111782
100782
100782
100782
92282
92282
92282
90982
90982
(continued)
205
-------
TABLE A.2. (continued)
Plot Oil Content
4 (con't) 1.05
, :--- 0.40
0.41
0.44
0.59
0.50
5 6.77
7.30
6.92
8.11
8.05
7.61
6.91
6.90
7.09
5.12
4.68
3.73
3.58
3.35
3.42
4.02
3.85
3.81
3.86
4.58
5.44
4.39
4.16
3.86
4.58
5.44
4.39
4.16
1.81
2.54
3.16
1.49
1.24
Date
90982
81082
81082
81082
81082
81082 .
60983
60983
60983
51083
51083
51083
111782
111782
111782
100782
100782
100782
92282
92282
92282
90982
90982
90982
81782
81782
81782
81782
81782
81282
81282
81282
81282
81282
81082
81082
81082
81082
81082
(continued)
206
-------
TABLE A.2. (continued)
Plot Oil Content
6 '. 9.68
* r-;; 15.26
10.14
8.13
8.29
8.06
10.59
10.24
9.37
11.92
11.39
10.13
9.32
9.02
10.12
7.98
12.27
8.63
7.80
8.17
5.59
3.07
5.74
5.60
5.74
7 5.08
4.83
4.90
4.76
4.40
4.45
3.71
3.68
3.69
4.24
4.57
4.36
2.82
2.79
3.27
2.73
3.45
3.05
Date
60983
60983
60983
60983
60983
60983
111782
111782
111782
101482
101482
101482
100482
100482
100482
81782
81782
81782
81782
81782
81082
81082
81082
81082
81082
60983
60983
60983
111782
111782
111782
100782
100782
100782
92382
92382
92382
92282
92282
92282
90982
90982
90982
(continued)
207
-------
TABLE A.2. (continued)
Plot
7 (con't)
-T ~
8
9
Oil Content
3.30
3.02
3.07
3.58
3.23
2.02
1.60
1.52
1.54
1.46
6.76
10.17
10.61
8.65
8.88
10.09
6.67
6.84
6.81
7.40
7.41
7.09
8.50
7.96
8.09
2.96
3.10
3.08
3.78
3.39
3.70
2.71
3.14
3.09
2.45
2.70
2.42
1.93
2.10
1.94
1.50
1.71
Date
81782
81782
81782
81782
81782
81082
81082
81082
81082
81082
60983
60983
60983
60983
60983
60983
111782
111782
111782
92682
92682
92682
91082
91082
91082
60983
60983
60983
51083
51083
51083
122082
122082
122082
111782
111782
111782
100782
100782
100782
92282
92282
(continued)
208
-------
TABLE A.2. (continued)
Plot Oil Content
9 (con't) 1.56
4 » = = 1.51
0.88
1.48
1.08
1.22
0.89
0.84
1.17
0.79
1.25
0.55
0.70
0.94
0.50
1.08
10 6.41
6.99
7.14
8.30
8.56
8.01
3.30
3.19
3.45
3.36
3.21
3.39
3.74
3.47
3.70
11 4.37
4.42
4.91
4.83
5.14
4.80
3.16
2.96
3.58
2.70
2.45
Date
92282
81282
81282
81282
81282
81282
81082
81082
81082
81082
81082
81082
81082
81082
81082
81082
60983
60983
60983
51083
51083
51083
110882
110882
110882
92682
92682
92682
91082
91082
91082
60983
60983
60983
111782
111782
111782
100482
100482
100482
90982
90982
(continued)
' 209
-------
TABLE A.2. (continued)
Plot
11 (eon't)
i =
12
13
Oil Content
2.63
2.95
2.69
2.94
2.79
2.65
1.66
1.39
1.58
1.50
1.67
0.10
0.06
0.09
4.65
4.76
4.14.
4.25
5.21
4.74
4.60
4.94
4.81
4.02
3.92
3.37
4.09
4.30
4.48
3.13
2.88
3.14
3.57
3.47
3.72
3.86
2.66
4.08
3.05
2.11
1.60
1.93
Date
90982
81782
81782
81782
81782
81782
81082
81082
81082
81082
81082
60983
60983
- 60983
60983
60983
60983
122082
122082
122082
111782
111782
111782
100782
100782
100782
92382
92382
92382
92282
92282
92282
90982
90982
90982
81382
81382
81382
81382
81082
81082
81082
(continued)
210
-------
TABLE A.2. (continued)
Plot
13 (con't)
± . ' '
14
15
Oil Content
2.88
3.07
2.00
2.21
2.15
2.52
2.69
2.88
2.15 .
2.07
2.15
1.47
1.32
1.29
1.03
0.97
1.01
1.62
1-.39
1.82
1.03
0.75
1.01
1.26
1.24
0.53
0.56
0.63
0.57
0.57
9.72
7.98
7.74
8.46
8.45
8.49
3.09
3.20
3.15
4.20
4.16
3.87
Date
81082
81082
60983
60983
60983
51083
51083
51083
111782
111782
111782
100782
100782
100782
92282
92282
92282
90982
90982
90982
81282
81282
81282
81282
81282
81082
81082
81082
81082
81082
60983
60983
60983
51083
51083
51083
110882
110882
110882
92682
92682
92682
(continued)
211
-------
TABLE A.2. (continued)
Plot
15 (con't)
i -u
16
17
18
Oil Content
3.99
3.98
4.16
5.34
5.51
5.43
3.20
3.31
3.48
3.99
4.01
4.02
. 4.07
4.12
4.01
2.91
2.45
3.16
1.80
1.92
1.77
2.74
2.21
2.31
2.21
3.35
2.70
1.27
1.33
1.58
1.83
1.50
1.41
1.46
1.46
1.60
0.96
1.17
0.99
1.13
1.11
Date
91082
91082
91082
60983
60983
60983
111782
111782
111782
92682
92682
92682
91082
91082
91082
60983
60983
60983
111782
111782
111782
92682
92682
92682
91092
91082
91082
60983
60983
60983
122082
122082
122082
111782
111782
111782
100782
100782
100782
92282
92282
(continued)
212
-------
TABLE A.2. (continued)
Plot
18 (.con't)
> / ' '
19
20
Oil Content
1.05
1.06
1.05
0.89
0.89
0.93
0.17
0.73
0.62
0.25
0.33
0.07
0.06
0.04
0.08
0.10
0.92
1.34
1.46
1.29
5.70
5.74
4.95
7.22
6.92
6.89
5.98
6.52
7.18
5.18
5.43
5.80
4.55
4.11
4.83
5.30
4.98
5.05
5.97
6.04
6.14
7.22
Date
92282
81382
81382
81382
81382
81382
81082
81082
81082
81082
81082
60983
60983
60983
51083
51083
51083
91082
91082
91082
60983
60983
60983
51083
51083
51083
111782
111782
111782
100782
100782
100782
92282
92282
92282
90982
90982
90982
81782
81782
81782
81782
(continued)
213
-------
TABLE A.2. (continued)
Plot
20 (.con't)
\ - . .
21
22
Oil Content
5.87
5.97
6.04
6.14
7.22
5.87
1.84
1.21
0.96
2.80
2.14
7.54
6.87
6.94
5.96
4.43
3.46
4.72
4.57
5.11
5.31
5.11
4.98
6.67
5.94
6.41
8.76
8.60
8.68
8.87
8.21
8.32
5.34
6.20
5.90
6.65
6.49
6.49
7.85
9.38
8.74
Date
81782
81282
81282
81282
81282
81282
81082
81082
81082
81082
81082
60983
60983
60983
111782
111782
111782
110982
110982
110982
92682
92682
92682
91082
91082
91082
60983
60983
60983
60983
60983
60983
111782
111782
111782
92682
92682
92682
91082
91082
91082
(continued)
214
-------
TABLE A.2. (continued)
Plot
23 .'.
* .*
24
25
Oil Content
7.50
7.39
4.30
2.93
3.70
2.29
7.91
7.85
8.31
8.24
8.42
8.32
9.81
10.02
9.34
7.18
4.14
4.13
4.53
4.60
4.53
4.47
4.77
1.76
1.60
1.85
1.90
2.00
1.83
2.79
2.59
2.80
1.10
1.32
1.34
2.02
1.90
1.83
1.64
1.52
1.49
1.51
Date
60983
60983
60983
122082
122082
122082
110982
110982
110982
92682
92682
92682
91082
91082
91082
60983
60983
60983
51083
51083
51083
111782
111782
110882
110882
110882
92682
92682
92682
91082
91082
91082
60983
60983
60983
51083
51083
51083
111782
111782
111782
100782
(continued)
' 215
-------
TABLE A.2. (continued)
Plot Oil Content
25 (con't) 1.39
::-- 1.32
1.72
1.38
1.69
1.19
1.21
1.21
1.38
1.98
1.62
1.47
1.50
1.61
1.39
1.43
1.47
1.50
1.61
1.39
1.43
0.28
0.57
0.66
0.90
0.54
26 5.18
5.18
4.82
2.89
2.65
5.11
5.04
5.36
3.88
4.67
4.77
4.34
4.28
4.00
4.73
4.37
4.49
4.19
4.83
Date
100782
100782
92382
92382
92382
92282
92282
92282
91082
91082
91082
81782
81782
81782
81782
81782
81282
81282
81282
81282
81282
81082
81082
81082
81082
81082
60983
60983
60983
122082
122082
111782
111782
111782
100482
100482
100482
90982
90982
90982
81782
81782
81782
81782
81782
(continued)
216
-------
TABLE A.2. (continued)
Plot
27 "
.=. r--
28
29
30
Oil Content
0.11
0.13
0.09
12.59
11.53
9.85
6.66
6.43
6.55
6.76
6.46
6.74
8.68
9.16
7.54
10.13
9.35
10.46
10.06
10.27
9.11
4.53
5.26
5.14
5.13
5.44
5.90
5.86
5.93
5.59
4.97
6.28
4.62
1.91
2.02
1.88
2.67
2.83
2.72
2.90
2.75
2.90
Date
60983
60983
60983
60983
60983
60983
110982
110982
110982
92682
92682
92682
91082
91082
91082
60983
60983
60983
51083
51083
51083
110982
110982
110982
92682
92682
92682
91082
91082
91082
51083
51083
51083
122082
122082
122082
111782
111782
111782
110882
110882
110882
(continued)
217
-------
TABLE A.2. (continued)
Plot
30 (con't)
.1 . .
31
32
Oil Content
3.18
3.14
3.13
4.39
4.91
4.19
2.12
1.81
1.68
1.61
1.61
1.77
1.84
1.91
1.99
2.31
1.92
1.76
2.31
2.11
2.39
1.90
1.80
1.82
2.57
2.16
2.57
2.76
2.87
2.90
2.32
2.03
2.19
2.05
2.25
3.32
2.56
2.80
2.94
1.86
2.15
2.02
2.14
Date
92682
92682
92682
91082
91082
91082
60983
60983
60983
111782
111782
111782
92682
92682
92682
91082
91082
91082
60983
60983
60983
122082
122082
122082
111782
111782
111782
101482
101482
101482
100782
100782
100782
100482
100482
100482
92382
92382
92382
92282
92282
92282
90982
(continued)
218
-------
TABLE A.2. (continued)
Plot
32 (.con't)
,t ;- -
33
34
35
Oil Content
2.25
2.12
2.36
2.56
2.23
2.32
2.46
0.11
0.12
0.11
4.04
4.05
4.50
4.20
4.15
4.32
2.83
3.41
2.74
4.77
4.81
4.59
2.74
2.70
2.92
3.11
3.11
3.09
1.71
2.80
1.78
3.17
3.58
6.62
6.17
4.69
2.56
2.54
2.33
3.74
3.83
3.40
Date
90982
90982
81782
81782
81782
81782
81782
60983
60983
60983
60983
60983
60983
51083
51083
51083
122082
122082
122082
101482
101482
101482
92282
92282
92282
90982
90982
90982
81282
81282
81282
81282
81282
51083
51083
51083
122082
122082
122082
111782
111782
111782
(continued)
219
-------
TABLE A.2. (continued)
Plot
35 (con't)
i -
36
37
38
39
40
Oil Content
3.84
3.82
3.95
4.15
2.45
2.23
5.13
5.36
5.63
8.00
7.03
6.94
3.98
3.23
6.39
8.57
8.18
8.52
0.08
0.12
4.73
4.29
3.32
2.46
2.82
2.67
3.56
3.59
3.35
0.06
0.06
0.05
0.05
0.08
0.05
0.08
0.04
0.08
0.07
0.06
Date
110882
110882
110882
92682
92682
92682
91082
91082
91082
60983
60983
60983
122082
122082
122082
91082
91082
91082
60983
60983
60983
60983
60983
110982
110982
110982
91082
91082
91082
60983
60983
51083
51083
51083
60983
60983
60983
51083
51083
51083
(continued)
220
-------
TABLE A.2. (continued)
Plot
41 .".
i ;- -
42
43
44
45
Oil Content
0.03
0.03
0.04
1.80
1.28
1.77
1.33
1.18
1.32
5.61
5.67
5.67
6.58
7.29
6.96
6.92
6,50
8.15
9.57
8.79
9.03
0.03
0.03
0.05
Date
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
60983
51083
51083
51083
60983
60983
60983
51083
51083
51083
110882
110882
110882
221
-------
TABLE A.3. TIME SERIES OIL CONTENT HISTORY
to
to
NJ
"
CT7D
2-8
58-
2.S
o
83
o
fi
BMS
ANALYSIS
DATE
82161
11932
71932
81732
9C932
1C0432
101432
101432
11C232
111732
111732
60933
(continued)
ELAPSED TIME
(CAYS)
,5?
332
361
334
334
409
419
419
438
453
453
657
nirtT ^ _
IDENTIFYING
CODE
L
L
L
L
B
H
E
J
A
F
B
H
c
OIL CONTENT
(X DUB)
.
7* 79
10172
9.61
9.73
12.23
12^50
15.00
10.82
OIL APPLIED
(X DWB)
1.25
2.50
2.93
2.93
2l93
2*50
2*50
2*50
s
-------
TABLE A.3. (continued)
to
to
OJ
ANALYSIS
DATE
82131
30932
71332
81782
9C932
92202
92332
92332
1CC7S2
1C1432
1CUc2
111782
111782
122082
12Z032
60983
ANALYSIS
DATE
R2181
12032
71332
312S2
90932
92232
1CC782
1C128?
11C282
111732
1 117*2
510-3
6C983
ELAPSED TIME
(DAYS)
C
151
199
32c
361
384
397
398
398
412
419
419
453
453
486
436
657
ELAPSED TIME
(DAYS)
0
152
326
356
384
397
398
412
417
438
453
453
627
657
IDENTIFYING
CCOE
L
L
L
L
L
E
3
H
A
9
H
A
B
H
B
H
E
IDENTIFYING
CCDS
L
L
L
L
E
B
H
B
H
F
B
H
c
E
OIL CONTENT
(X DW3)
m
m
m
m
3.99
3.33
4.12
3.90
3.57
5.77
5.64
5.10
6.34
5.08
6.33
6.76
OIL CONTENT
(X DUB)
9
m
9
m
1.03
0.98
1.55
1.31
1.71
K74
2.32
2.25
1.62
(X DWB)
0.831
1.245
1.245
1.245
1.245
m
9
C.290
m
2.200
1.245
U245
OIL APPLIED
(X DWB)
0.2875
0.5750
0.575C
0.5750
0.5750
Ol4070
0.575
Cl575
(continued)
-------
TABLE A.3. (continued)
NJ
ANALYSIS 1
DATE
32131
12032
71382
31232
9093'
92222
92332
10C732
101232
110732
111782
111732
51083
60933
FMS5f? TIME
0
III
356
384
397
398
412
417
438
453
453
627
657
PLOT=5
IDENTIFYING
CODE
L
L
L
L
E
3
H
8
H
F
B
H
E
E
OIL CONTENT
U OWB)
m
3.89
3.45
5.37
4.90
6.82
6 97
8l89
7.92
7.00
CIL APPLIED
(X DUB)
0.863
1.920
1.920
1.920
K920
K920
2.500
K920
m
S"?1
ANALYSIS
DATE
S21S1
11932
41532
71932
?17S>
91062
100482
101432
1014^2
111782
111782
60933
ELAPSED TIME
(DAYS)
0
151
237
332
361
335
409
419
419
453
453
657
PLOT=6
IDENTIFYING
CODE
L
L
L
L
L
F
E
J
A
B
H
E
OIL CONTENT
(X OMB)
9.49
9.15
11.65
10.07
12.57
8.16
1.246
2.500
2.500
2.930
2.930
2.930
2.500
2^500
(continued)
-------
TABLE A.3. (continued)
ro
ui
ANALYSIS
DATE
«2131
11982
42032
72032
B17S2
90932
92282
92352
9235?
100732
101232
111732
111762
6C933
ANALYSIS
DATE
32131
1 1 9 < 2
91082
92662
111782
111782
6C9b3
ELAPSED TIME
(DAYS)
0
151
252
333
361
334
397
393
398
412
41 7
453
453
657
ELAPSED TIME
(D.AYS)
0
151
335
401
453
453
657
- KLUi=r ------
IDENTIFYING
CODE
L
L
L
L
L
E
6
H
A
B
H
3
H
E
IDENTIFYING
CODE
L
L
c
E
a
H
E
OIL CONTENT
(X DUB)
.
3.08
2.80
3.95
4.30
3.69
4.84
4.54
5.69
4.94
OIL CONTENT
(X OUB)
alia
7.30
6.77
14.25
9.68
OIL APPLIED
(X DUB)
0.479
1.150
1.150
1:li8
1.150
9
1.150
1.150
OIL APPLIED
(X Qwa>
7.475
1 1 .550
«
7.745
(continued)
-------
,3. (continued)
to
ANALYSIS
CAT- I
821*1
12032
30332
71332
81232
92282
92332
102782
110732
111782
111732
122082
1 ? '0 **'
510d3
60933
ANALYSIS
DATE
? 2 1 d 1
12032
72032
91032
9265?
1108S2
11C93?
51033
60983
ELAPSED TIME
(DAYS)
C
152
199
326
356
397
393
412
433
453
453
486
436
627
657
ELAPSED TIME
(DAYS)
0
152
333
335
401
444
445
627
657
IDENTIFYING
CCDE
L
L
L
L
L
B
H
B
F
3
H
B
H
E
E
IDENTIFYING
CCDE
L
L
L
E
E
B
H
E
E
OIL CONTENT
(X DUB)
^
m
m
1.59
2.16
1.99
2l52
3.10
2.98
3.55
5.05
OIL CONTENT
(X DUS)
-
m
3.64
3.32
3.31
10.21
8.29
6.85
OIL APPLIED
(X DUB)
0.319
C.575
0.575
C.575
0.575
CI575
d575
01575
Cl575
OIL APPLIED
(X DUB)
0.96
3.45
3.45
"
6l90
(continued)
-------
to
eo
ANALYSIS
DATE
?2131
11932
71932
81782
9C982
9108?
10C432
101282
11C2S2
111782
111782
60933
ANALYSIS
DATE
82161
12082
30382
42C3?
72032
81?32
90982
92282
92332
92332
100732
101282
111732
111732
122022
122332
6C933
TABLE
ELAPSED TIME
(DAYS)
C
151
332
361
384
385
409
417
434
453
453
657
ELAPSED TIME
(DAYS)
0
152
199
252
333
356
384
397
398
398
412
417
453
453
486
436
657
A. 3. (continued
IDENTIFYING
CODE
L
L
L
L
B
H
E
F
F
B
H
E
IDENTIFYING
CODE
L
L
L
L
L
L
E
3
H
A
B
H
B
H
3
H
E
)
OIL CONTENT
(X OW8)
2.59
3.74
3.23
4.92
6.07
4.57
OIL CONTENT
(X DUB)
3.58
3.05
4.01
4.29
3.97
4.92
4.78
5.74
4.73
5.69
4.51
OIL APPLIED
(J DUB)
0.479
1.150
1.150
1.150
1.150
1 .150
1.150
1.150
OIL APPLIED
(X DUB)
0.575
0.958
0.958
0.958
0.958
C.958
0.958
0.958
0.958
0.958
(continued)
-------
TABLE A.3. (continued)
K>
M
oo
Is-
ffl :r
o
o!
x>
ANALYSIS
DATE
821 32
1203?
71332
31232
9G932
02252
92382
1CC7S2
101P32
110232
111782
111782
51083
60933
ANALYSIS
DAT:
92131
12082
7 1 3 S 2
9108?
92632
11C3£2
110932
51083
60933
ELAPSED TIME
(DAYS)
0
152
332
356
334
397.
398
412
417
433
453
453
627
657
?LAPSEO TIME
(DAYS)
0
152
332
385
401
444
445
627
657
- KLUI=1*
IDENTIFYING
CODE
L
L
L
L
c
8
H
3
H
F
B
H
E
E
IDENTIFYING
CODE
L
L
L
E
p
§
H
E
E
OIL CONTENT
U DUB)
1.61
1.00
1.58
1.36
1.93
2.12
2.70
2.70
2.12
OIL CONTENT
11 OWB)
4.C4
4.08
3.15
10.05
8.47
7.88
OIL APPLIED
11 DUB)
C.2875
0.5750
C.5750
0.5750
0^5750
0^5750
C.5750
0.5750
*
OIL APPLIED
1% DUS)
. 0.958
3. 450
3.450
*
6.900
«
(continued)
-------
TABLE A.3. (continued)
to
ANALYSIS
DATE
82131
119fc2
91032
92682
111732
111732
60933
ANALYSIS
DATE
82131
11982
91032
92682
111782
111732
6C933
ELAPSEO TIME
(DAYS)
0
151
385
401
453
453
657
ELAPSEO TIME
(DAYS)
0
151
3?5
401
453
453
657
- KLUI=10
IDENTIFYING
CODE
L
L
E
E
8
H
E
SAS
IDENTIFYING
CODE
L
L
E
E
B
H
E
OIL CONTENT
-------
TABLE A.3. (continued)
to
OJ
o
ANALYSIS
DATE
32181
11982
30832
71332
31232
922d2
02322
1C0732
101232
110P82
111782
111782
122032
122082
60933
ANALYSIS
DATE.
32181
1C?32
41532
72082
"1232
90932
92232
92332
100782
101232
1 1 1 7 ? 2
111732
51033
60933
ELAPSED TIME
(DAYS)
0
151
199
326
356
397
393
412
417
438
453
453
486
486
657
ELAPSED TIME
(DAYS)
0
152
247
333
356
334
397
398
412
417
453
453
6?7
657
IDENTIFYING
CODE
L
L
L
L
L
B
H
B
H
f
B
H
B
H
E
IDENTIFYING
CODE
L
L
L
L
L
E
B
H
5
H
3
H
E
E
OIL CONTENT
(X DWB)
m
m
9
1.10
.39
.04
.33
151
.79
.45
.39
OIL CONTENT
(X DWS)
.
.
,
m
5.11
4.50
6.42
5.47
7.39
6.56
8.48
7.01
5.46
OIL APPLIED
(X OWB)
C.1900
0.2375
0.2375
0.2875
0.2375
0^2875
012875
0.2875
Ol2875
^
0.2875
OIL APPLIED
(X DWB)
0.863
1.920
1.920
1.920
1.920
.
»
1.920
,
1 .920
«
1.920
,
(continued)
-------
TABLE A.3. (continued)
PLOT=21
ANALYSIS ELAPSED TIME IDENTIFYING
DATE (DAYS) CODE
?2181 0 L
119*2 151 L
91032 335 E
92432 4G1 E
110952 445 E
111782 453 B
111782 453 H
60953 657 E
OIL CONTENT
(X DWB)
5.13
4.80
4.62
12.09
7.12
OIL APPLIED
(X DUB)
7.475
7.420
7.475
to
ANALYSIS
CATE
C21d1
11952
91C3?
92632
111782
111732
60983
ELAPSED TIME
(DAYS)
0
151
3*5
401
453
453
657
HLUI=£<: ------
IDENTIFYING
CODE
L
L
E
E
B
H
E
OIL CONTENT
(X DUS)
8.66
6.54
5.81
11.56
8.57
OIL APPLIED
(X OU9)
5.18
11.50
m
,
5.75
(continued)
-------
TABLE A.3. (continued)
to
u>
eo
-TJO
a a
2."°
?8-
I.S
I2-
ID
O
ANALYSIS
SATE
82181
12052
72032
91C32
9253?
110952
1?2082
60983
ANALYSIS
DATE
82181
12C82
7133?
9103?
92662
110832
110932
111762
51083
60983
ELAPSED TIME
(CAYS)
0
152
333
385
401
445
436
657
ELAPSED TIME
(DAYS)
0
152
332
335
401
444
445
453
627
657
- PLOT=
-------
TABLE A.3. (continueu)
to
u>
ANALYSIS
DATE
82131
120
-------
TABLL A.3. (continued)
to
U)
ANALYSIS
OATS
82131
12082
72032
910*2
92632
11C932
110932
60983
ANALYSIS
DATS
32181
12032
72032
91082
92682
11C932
1109S2
51083
60983
ELAPSED TIME
(DAYS)
0
152
333
385
401
445
445
657
ELAPSED TIME
(DAYS)
0
152
333
385
401
445
445
627
657
- PLUI =
-------
TABLE A.3. (continued)
to
U>
Ul
ANALYSIS
DATE
82181
12082
91082
926S2
110*32
111782
122G32
122032
4 1 1 ? 3
51083
60983
ANALYSIS
DATE
32181
11932
91082
92682
111782
6C983.
ELAPSED TIME
(DAYS)
0
152
m
444
453
486
486
593
627
657
ELAPSED TIME
(DAYS)
0
151
385
4C1
453
II?
- PLOT=30
IDENTIFYING
CODE
L
L
E
E
E
B
H
E
E
E
IDENTIFYING
CODE
L
L
E
E
B
H
E
OIL CONTENT
(X DUB)
i:?S
j j
2 85
t~ m \j J
2.74
1.94
5.39
5. 20
* k W
4 79
" f T
2.51
OIL CONTENT
(X OUB)
9
m
2.00
1.91
1.66
i:H
OIL APPLIED
(X OUB)
5.75
6.90
3.'45
OIL APPLIED
(X DUB)
3.450
3.450
.
.
0
1.725
(continued)
-------
TABLE A.3. (continued)
N)
u>
CTi
i n
^o
ANALYSIS
DATE
32131
11932
3G8S2
42082
81722
9C982
922i?
92332
923H2
10C4S2
1CC782
101432
101432
111782
111732
122032
122032
60993
ELAPSED TIME
(DAYS)
0
151
199
252
361
384
397
393
398
409
412
419
419
453
453
486
486
657
KLUI =ic
IDENTIFYING
CODE
L
L
L
L
L
E
a
H
A
E
E
J
A
B
H
6
H
E
OIL CONTENT
(X DUB)
2.17
2.01
2.58
2.77
2.54
2.13
2.27
2.84
2.43
3.01
1.84
2.15
2.27
OIL APPLIED
(X ous)
0.319
0.575
C.575
0.575
0.575
9
0.575
*
0.575
0.575
0.575
(continued)
O :
o
-------
TAJbLr. A.
( continued )
10
u>
-j
ANALYSIS
DATE
32131
11932
30832
41532
71332
81232
Q09o2
92T32
92352
10U32
1C14S2
122082
1?20&2
51083
60983
ANALYSIS
DATE
32131
12C32
91032
92*42
110832
111782
122032
12 20* 2
41183
51083
6C963
ELAPSED TIME
(CAYS)
0
151
199
237
326
356
384
397
393
419
419
436
436
627
657
ELAPSED TIME
(DAYS)
0
152
385
401
444
453
436
486
593
627
657
- KLUt=i<»
IDENTIFYING
CODE
L
L
L
L
L
L
E
3
H
J
A
3
H
E
E
IDENTIFYING
CCDE
L
L
E
E
p
E
6
H
c
E
E
OIL CONTENT
<% OMB)
3.10
2.79
3.74
3.77
4.72
2.99
3.95
4.22
4.19
OIL CONTENT
(% DUB)
5.37
4.14
3.87
3.66
2.48
8.23
7.82
6.40
5.24
OIL APPLIED
(X DWB)
0.575
0.958
0.958
C.958
0.958
C.958
9
«
0.958
0.958
0.958
OIL APPLIED
(X ows)
5.175
6.807
«
5.750
«
(continued)
-------
t\. 3. (con cinueu)
u>
CD
ANALYSIS
CATS
921S1
1196?
71932
91082
122032
122982
dC9S3
ANALYSIS
DATE
*21
-------
TABLE A.4. RAW FRACTIONATION DATA - PLOTS 30 and 35
Plot
30 -
35
Elapsed
Day
385
385
385
401
401
401
444
444
444
486
486
486
598
598
598
627
627
627
657
657
657
385
385
385
401
401
401
444
444
444
486
486
486
598
598
598
627
627
627
657
657
657
%
Oil
In Soil
4.39
4.91
4.19
3.18
3.14
3.13
2.90
2.75
2.90
1.91
2.02
1.88
4.26
5.60
9.47
5.40
5.15
4.75
2.57
4.51
2.49
5.13
5.36
5.63
4.15
4.33
4.63
3.84
3.82
3.95
2.56
2.54
2.33
8.42
6.07
8.98
6.97
6.35
6.23
5.11
3.42
5.38
%
Asph.
In Oil
4.68
4.10
4.88
5.81
6.11
5.79
8.85
8.64
8.32
3.90
3.20
5.71
5.34
5.66
5.15
5.85
6.03
7.56
4.00
5.43
4.61
6.94
5.70
4.48
8.26
8.32
9.76
4.37
6.18
4.89
7.75
5.65
6.69
6.49
6.84
7.43
4.90
5.36
5.87
%
Sat.
In Oil
48.46
43.27
48.30
40.45
40.32
41.50
30.63
29.94
36.49
23.84
15.70
19.45
33.40
30.59
30.92
42.61
35.33
31.46
48.51
35.11
19.28
44.21
43.22
43.22
30.69
24.67
28.83
20.27
20.34
22.90
33.16
41.72
36.40
38.07
44.62
12.68
%
Arom.
In Oil
30.74
30.74
30.74
28.20
28.20
28.20
27.33
26.85
12.29
36.72
55.03'
33.70
24.66
27.20
27.27
13.66
28.15
31.19
20.59
12.52
35.95
24.97
30.32
23.77
36.72
35.32
35.05
21.27
19.68
19.69
31.43
11.40
31.43
%
Polar
In Oil
19.12
16.85
24.34
25.43
24.83
25.12
33.20
34.57
42.90
35.54
26.07
41.15
36.59
36.55
36.66
39.72
31.09
23.97
44.67
40.29
36.21
37.49
37.49
36.08
38.69
37.64
38.15
4.92
19.07
37.82
32.95
21.10
25.59
38.29
25.59
239
-------
TABLE A.5LEGEND FOR FIGURES A.I to A.32
A 'After' application sample
B 'Before1 application sample
E 'Extra1 sample not associated with application
F "Failed1 to sample on application date
H 'Hypothetical After1 sample
J 'Hypothetical Before1 sample
L 'Loading' only, no sample
240
-------
15-1
11-
13-
C 12
0
N
T
E
N li
T
10-
0
R
T
S 5'
0
I
L
H S-|
£
I
G
H
T 7
6-
\
k
\
\
\
\
\
300 350 100
LEIENO: CODE
USD 500 550
ELRPSEO TIME (DOTS)
600
650
700
f * » 8
x x x J
* + + E
x x x L
* * * F
Figure A.I. Time series oil content history, plot 1
Reproduced from
best available copy.
241
-------
6.5-
6.3-
0 6.0-
1
L
C 5.7-
0
N
T
E 5.4-
N
T
( 5.1-
7.
D
R H.8-
I
S
0 U.5-
I
L
W 4.2-
E
I
3.6-
3.3-1
3.0-
300 350 400
450 500 550
EL3PSED TIME (DflTS)
600 650
700
LEGEND: CODE
-t- H
* * * H '.
Figure A.2. Time series oil content history, plot 2,
242
-------
2.3-
2.2-
2.1-
2.0-
C 1.8-
0
N
T 1.
E
N
T 1.6-1
7. 1.5H
0
fi 1.4-
T
S 1.3-
0
I
L 1.2-
M
E l.
!
G
H 1.0-
T
)
0.9-
o.e-
0.7-
0.6-
700
300 350 400 450 500 550 600 650
ELflPSED TIME (D9TS)
LEGEND: CODE + + + B »»»£ * + + F +*#H *#«L
Figure A.3. Time series oil content history, plot 4
243
-------
9. OH
8.5-
8.0-
0
I
L 7.5
C
0
N 7.0
T
E
N
T 6.5
X
6.0
0
R
Y
5.5.
5
0
I
L 5.0
M
E
I "i.5-
G
H
T
) 4.0-
3.5-
3.OH
300
LEGEND: CODE
\
350 400
+ + + 8
150 500 550
ELflPSEO TIME (OflTS)
600 650
***H
700
Figure A.4. Time series oil content history, plot 5,
244
-------
13.0-
12.5-
12.0-
0 :
L ;
C 11.5-
0 :
N :
T :
E :
N 11.0-
T ;
10.5-
D :
R :
T ;
S 10.0-
0 :
L ;
W 9.5-j
E :
G :
H :
T 9.0-
8.5-
8.0-
i
t
K
\
\
\
\
\
,
\
\
\
\
\
^ \
\
1 \
\
\
300 350 400 U50 500 550 600
ELflPSEO TIME (OflTS)
LEGEND: CODE
+ + + R -f-f + B * + + E
H xxxj xxxL
650 700
* * « F
Figure A.5. Time series oil content history, plot 6,
245
-------
5.75-J
5.50-
5.25-
0 5.00
I
L
C 4.75
0
N
T
E 1.50
N
( 4.25
X
D
R 4.00
T
S
0 3.75
I
L
W 3.50
E
I
G
H 3.25
T
3.00-
2.75-
2.50-
300 350 400
LEGEND: CODE
+ + + fl
450 500 550 600
ELflPSED TIME (DflTS)
+ + + B * * * E * * * H
650
700
Figure A.6. Time series oil content history, plot 7.
246
-------
15-
13-
0
I
L
C 12
0
N
T
E
N 11
T
10-
0
R
r
S 9
0
I
L
H 5'
E
I
G
H
T 7
5-
N
»
\
\
\
\
\
\
\
300 350 UOO
LEGEND: CODE
450 500 550
ELflPSED TIME (DflYS)
600 S50 700
* « » L
Figure A.7. Time series oil content history, plot 8.
247
-------
3.6-
3.4-
3.2-
C 3.0
0
N
T
E
N 2.8
T
2.6-
S 2.4
0
I
L
U 2.2
E
I
G
H
T 2.0
1.8-
1.6-
\
300 350 400
LEGEND: CODE + + + B
450 500 550
ELflPSED TIME (DflTS)
600 650 700
L
Figure A.8. Time series oil content history/ plot 9,
248
-------
10-
9-
0 8-
I
L
C
0
N
T
E
N
T 6
7-
5-
HI
E 3-
I
G
H
T
) 2-3
1-
0-
300 350 400
LEGEND: CODE
450 500 550 600 650 700
ELflPSEO TIME (OflTS)
+ B »»»£ ***H *«*L
Figure A.9. Time series oil content history, plot 10.
249
-------
6.3-1
6.0-
5.7-
0 5.4-
1
L
C 5. 1-
0
N
T
E 1.8-1
N
T
( 4.5-
X
s
3 3.9-1
I
L
M 3.6-1
E
I
G
H 3.3-
T
3.0-
2.7-
2.4-
\
\
»
\
\
t
\
700
300 350 400 450 500 550 600 650
ELflPSED TIME (OPTS)
LEGEND: CODE +++6 +++E +++F « * » H * L
Figure A.10. Time series oil content history, plot 11.
250
-------
5.75-
5.50-
0 5.25
I
L
C 5.00'
0
N
T
E 4.75
N
T
( 4.50
X
0
R 4.25.
Y
0 H.OO
I
L
H 3.75
E
I
G
H 3.50
3.25-
3.00-
|.......r.(.T,.....,,..
300 350 400
LEGEND: CODE + + + B
450 500 550 600 650 700
ELflPSED TIME (ORTS)
+ + + B »»»£ * « » H L
Figure A.11. Time series oil content history, plot 13.
251
-------
2.7-
2.5-
2.4-|
0 :
I 2.3-
L :
C 2.2-
o :
N
T 2.1-
E :
N :
X. 1.9-|
0 :
a 1.8-
T :
S 1.7-
o :
i
L 1.6-
H
E 1.5-
i :
G
H 1.4-
T :
1.3-|
1.2-
1. l-
1.0-
300 350 400 450 500 550
ELflPSED TIME (OflTSJ
_EGEND: CODE + f B *f + E * + »F
600
650
700
L
Figure A.12. Time series oil content history, plot 14,
i 252
-------
10-
9-
8-
7-
6-
5-
4-
3-
2-
1-
OH
300 350 400
LEGEND: CODE
450 500 550
ELflPSED TIME (OflTS)
+ B -f + *E
600
650
700
Figure A.13. Time series oil content history, plot 15.
253
-------
6.9H
6.6-
6.3-
Q 6.0-
I
L
C 5.7-
0
N
T
£ 5.4-
N
T
( 5.1-
X
0
R "4.8-
T
S
0 14.5-
I
L
H 4.2-
E
I
G
H 3.9-
T
3.6-
3.3-
3.0-
»
300 350 1400
LEGEND: CODE
USD 500 550
ELRPSED TIME (DflTS)
600 650
700
*«*L
Figure A.14. Time series oil content history, plot 16,
254
-------
3.6-1
3.4-
3.2-
C 3.0-
0
N
T
E
N 2.8-
T
2.6-
S 2.4-
0
I
L
H 2.2-
E
I
G
H
T 2.0-
1.8-
1.6-
\
\
300 350 400
LEGEND: CODE
450 500 550
ELflPSED TIME (OflTS)
600 650 700
#*«L
Figure A.15. Time series oil content history, plot 17.
255
-------
1.7-
0
I
L 1.6
C
0
N
T
E 1.5
N
T
(
X
D
R
T
S
0 1.3
I
L
H
E
I 1.2
G
H
T
1. 1-
1.0-
300 350 400
LEGEND: CODE + + + 8
150 500 550 600 650
ELRPSED TIME (DRTS)
» + »£ + * + F «»*H
700
Figure A.16. Time series oil content history, plot 18.
256
-------
8.5-1
8.0-
0
1
L 7.5-
C
0
N
T
E 7.
N
T
6.5-
6.0-
5.5-
5.0-
U.5-
300 350 HOD U50 500 550
ELfiPSEO TIME (DflYS)
600
650
700
LEGEND: CODE
*»*H
***L
Figure A.17. Time series oil content history, plot 20.
257
-------
12-
11-
10-
0
I
L
C 9
0
N
T
E
N 8
T
7-
D
R '
T
S 6'
0
I
L
H 5
E
I
G
H
T 4
3-
2-
\
\
\
300 350 HOO
LEGEND: CODE
U50 500 550 600 650 700
ELflPSED TIME (DflTS)
t-B «*»£ + » # H ««*L
Figure A.18. Time series oil content history, plot 21.
258
-------
12.0-
11.5-
11.0-
0 10.5-
I
L
C 10.0-
0
N
T
E 9.5-
N
T
( 9.0-
X
D
R 8.5-
T
S
0 8.0-
I
L
* 7.5-
E
I
G
H 7.0-
T
6.5-
6.0-
5.5-
\
k
\
\
\
b
\
\
\
300 350 400 450 500 550 600 650 700
ELRPSEO TIME IDRYS)
LEGEND: CODE + + + B +»»£ +**H ***L
Figure A.19. Time series oil content history, plot 22,
259
-------
9.9-1
9.6-
9.3-
0 9.0-
I
L
C 8.7-
0
N
T
E 8.U-
N
T
( 8.1-
X.
0
R 7.8-
T
S
3 '7.5-
I
L
W 7.2-
F
T
G
H 6.9-
T
6.6-
6.3-
6.0-1^
300
350 HOO H50 . 500 550
ELflPSEO TIME (DflTS)
LEGEND: CSDE + + » E +«
600 650 700
* + + L
Figure A.20. Time series oil content history, plot 23,
260
-------
5.1-
4.8-
0 4.5
1
L
C 4.2
0
N
T
E 3.9
N
( 3.6-
X
D
H 3.3
T
3 3.0.
I
L
W 2.7.
E
I
C
H 2.4
T
2.1-
1.8-
1.5H
300 350 400
LEGEND: CODE
450 500 550
ELflPSED TIME (CRTS)
+ B + + + E
600 650
700
**»L
Figure A.21. Time series oil content history, plot 24,
261
-------
1.9-1
1.8-
0
I
L 1.7
C
0
N
T 1.6
E
N
T
( 1.5'
X.
0
R
T l.U-
S
0
I
L 1.3-
H
E
I
G 1.2
H
T
1. 1-
1.0-
300 350 400
LEGEND: CODE + + + fl
450 500 550
ELflPSEO TIME (DflTS)
SOO 650 700
+ * * H * L
Figure A.22. Time series oil content history, plot 25,
262
-------
6.6-1
6.3-
6.0-
0 5.7-
I
L
C 5.4-
0
N
T
E 5.1-
N
( 4.8-
I.
0
R 4.5-
T
S
0 4.2-
I
L
W 3.9.
E
I
G
H 3.6-
T
3.3-
3.0-
2.7-
X
300 350
.EGENO: CODE
400 450 500 550
ELRPSED TIME IDfiTS)
+ B »»»£ * + *F
600 650
700
L
Figure A.23. Time series oil content history, plot 26,
263
-------
19H
18-
17-
0 16
I
L
C 15
a
N
T
E m.
N
T
( 13-
D
R 12
T
S
0 11
I
L
U 1C
E
I
G
H 9
T
8-1
7-
\
h
\
\
\
300 350 400 USD 500 550 600 650 700
ELRPSED TIME (DOTS)
LEGEND: CODE + -t- + B +ȣ + + + H ***[_
Figure A.24. Time series oil content history, plot 28.
264
-------
16-1
15-
0
I
L m.
c
o
N 13
T
E
N
T 12
11-
10-
9-
M
E
I 8.
G
H
T
) 7-
6-
300 350 100
LEGEND: CODE
USD 500 550 600 650 700
ELflPSEO TIME (CRTS)
+ B »» + £ *» + H *««L
Figure A.25. Time series oil content history, plot 29,
265
-------
5.u-l
5.1-
1.8-
0 14.5-
1
L
C 14.2-
0
N
T
E 3.9-
N
T
( 3.6-
X
D
R 3.3-
T
S
0 3.0-
I
L
H 2.7-
E
I
G
H 2.4-
T
2.1-
1.8-
1.5-
300 350 400
LEGEND: CODE
450 500 550 600 650
ELflPSED TIME (DflTS)
+ B » + » E ***H **
700
Figure A.26. Time series oil content history, plot 30,
266
-------
3.4-
3-2-:
3.0-
0 j
L ;
C 2.8-
0 :
N :
T :
E :
N 2.6-
T :
X :
2.4-
D :
R :
T j
S 2.2^
o ;
L ;
M 2.0-
E
I
G
H
T 1.8-
1.6-
1.4-
\
\
\
\
\
\
\
\
A
\
\
\ .
\
300 350 400
LEGEND: CODE
450 500 550
ELRPSED TIME (OflTS)
600 650 700
*«»!_
Figure A.27. Time series oil content history, plot 31,
267
-------
3.0-
2.9-
2.8-1
0
I
L
2.7-1
C
0
N
T 2.6-1
E
N
T
2.5-1
D 2.H-
R
T
S 2.3-
0
I
L
2.2-j
M
E
I
G 2.1-1
H
T
)
2.0-J
1.9-
1.8-
300 350
>400
U50 500 550
ELflPSED TIME (DRTS)
LEGEND: CODE
*!* B
* * + H
* * + 8
* J
600 650
* » » c
x x x L
700
Figure A.28. Time series oil content history, plot 32
268
-------
4.8-1
U.6-
4.U-
0
I
L
C U.2-
0
N
T
E
N il.O-
T
3.8-
S 3.6-
0
I
L
H 3.4-
E
I
C
H
T 3.2-
3.0-
2.8^
300
350
100
450 500 550
ELflPSED TIME (DfllTS)
600
650
700
LEGEND: CODE
* R
« H
*» B
J
* * * E
x x x L
Figure A.29. Time series oil content history, plot 34,
269
-------
3.0-
7.5-
0 7.0-
I
L
C 6.5-
0
N
T
E 6.0-
N
T
( 5.5-
X.
0
R 5.0-
T
S
0 14.5-
1
L
14.0-
3.0-
2.5-
2.0-
300 350 400
LEGEND: C30E
1450 500 550
ELRPSED TIME (DflTS)
+ B +»«£
600
650 700
***L
Figure A.30. Time series oil content history, plot 35
270
-------
8.5-
8.0-
0
I
L 7.5-
C
0
N
T
E 7.0
N
T
6.5-
S
3 6.0
I
L
M
E
I 5.5
G
H
T
5.0-
U.5-
300 350 400 450 500 550
ELflPSED TIME (DflYS)
LEGEND: CODE -f + -f B +» + £
600 650 700
*M *«*L
Figure A.31. Time series oil content history, plot 36,
271
-------
6.0-
5.5-
0
I
L 5.0
C
0
N
T
E 4.5
N
T
4.0-
S
3 3.5
I
L
W
E
I 3.0-
G
H
T
2.5-
2.0-
\
300 350 400
LEGEND: CODE
450 500 550
ELflPSED TIME (DflTS)
+ B +»*£
600 650 700
»**L
Figure A.32. Time series oil content history, plot 38.
272
-------
APPENDIX B
VOLATILE EMISSIONS DATA
.273
-------
TABLE B.I.
CALCULATED EMISSION RATES OF TOTAL
VOLATILE HYDROCARBONS FOR FIELD
EXPERIMENTS
Date
of
Sampling
07/19/62
07/19/82
07/19/62
07/20/62
07/21/62
05/02/32
06/17/62
06/17/62
oe/:'/32
09/17/S2
08/17/62
06/17/82
08/22/52
08/31/92
09.'0:/92
OS/02/52
CS/05'52
OS/:0/52
C9/1C/32
05/10/62
09/: :/52
OS/21/92
10/07/32
10/07/32
lO/l-i/62
10/14/52
ic.' i4/?j
1C/J4/52
10/15/82
1C/-.7/52
10/21/82
1 C / 2 '. / 5 2
10/26/52
1 1/02/52
11/02/52
11/02/62
11/02/52
1/C2/52
1/02/52
1/02/82
1/03/82
1/05/62
1/09/92
1/17/E2
1/17/82
1/17/92
1/17/S2
1/17/92
1 / !9/32
11/24/62
12/20/62
07/20/62
07/20/32
07/20/82
07/21/62
07/25/92
Q5/0-5/S2
OS :2/';2
Oc.-::v52
Nominal Rate Vola.
Loading of of
Plot Rate Sampling* Emis. Slud.
No. (%) Status (g/hr) (%)
l
l
l
l
l
i
i
i
;
i
1
1
1
1
1
1
1
1
1
t
i
i
i
i
i
i
i
i
^
j
i
;
1
;
1
;
1
j
j
1
i
i
;
1
*
6
5
5
6
5
5
C
13
13
13
13
13
13
i 3
13
13
13
13
13
'. 3
13
13
13
13
13
13
13
13
13
13
1 3
; 3
13
13
13
13
13
13
13
13
13
13
13
1 3
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
3
3
3
3
3
RT
RR 1
IRT.RR
BETR
BE'R
BETR
BT
RT
Rr2
5RR
IPT.PS
2CRT.RR
BCTR
BETfl
RT
9CRT
120RT
BETfl
RP3
IPT.RS
BETR
BETS
BT
RT
BETR
BETfi
PflH
IPT.flS
BETS
BETP
BT
RT
BETR
BT
RT.BR
RR5
IST.flfl
2k-a.flT
UHn.flT
6HF..RT
2ETR
BETfi
BETR
BT
RT
RP.6
3CRT.RR
4HRRP.R
24HR.RR
BE'fl
BETR
BR
RR1
RT.flfl
BETfl
BETR
EETR
gs- a
BETR
7.
lie.
96.
24.
14 .
i :.
7.
13.
1 O
Ii!
19.
19.
12.
11.
18.
16.
15.
11.
35.
40.
19.
13.
10.
17.
11.
19.
409.
150.
57.
25.
IS.
3S.
11.
11.
38.
367.
402.
325.
255.
195.
65.
29.
26.
10.
15.
72.
62.
35.
15.
5.
3.
7!
112.
96.
24.
11.
5.
c
c _
90
47
69
57
50
70
50
15
as Q
w « w
45
50
50
43
70
25
33
69
70
10 8
22
93
1 5
61
55
70
65
52 14
14
51
26
09
49
70
70
36
69 13
51
15
25
26
01
25
33
82
15
57 9
77
11
13
95
21
90
50
67
57
SO
12
i >
12
Soil
Mois. Soil
Cont. Temp.
f
27 .
t
t
.
.
t
2U
24.
24.
20.
20.
18.
17.
15.
.
.
,
B
.
.
.
29.
t
23.
24.
21.
,
g
.
m
t
.
m
t
,
t
28.
28.
m
t
.
t
.
.
.
.
.
.
.
17.
17.
17.
i^
2
c
9
=
0
1
5
4
7'
i
^
Q
8
8
3
?
'-
90
91
S:
SO
65
92
87
87
8E
67
o :
si
67
84
03
si
91
76
75
86
67
85
90
64
34
84
63
80
79
75
76
T>
69
56
69
77
77
77
77
75
68
65
50
55
55
50
50
51
44
41
90
90
90
81
62
9:
105
1 05
Rela.
Humid.
57
54
54
57
58
58
65
66 .
c:
65 '
75
76
35
39
20
2!
48
49
56
85
62
6 1
40
45
60
6!
62
73
65
55
35
71
31
35
38
77
65
85
84
84
SO
61
58
60
84
84
85
82
70
50
43
56
56
55
55
50
35
33
63
(continued)
274
-------
TABLE B.I. (continued)
.:
Date
of
Sampling
05/10/82
06/17/£2
08/17/62
06/17/52
08/26/62
06/21/82
OS/31/32
05/02/52
OS/CS- 52
05/CS/52
09/10/52
CS/:0/52
OS/ i 1/52
05/21/92
10/07/52
10/07/82
10/14/82
10/14/82
10/14/52
10/14/82
10/15/82
10/17/S2
10/21/82
10/21/92
10/25/62
11/02/52
11/02/82
11/02/52
11/02/82
ll/:3/92
11/35/92
11/C9/52
11/17/52
11/17/S2
11/17/82
11/17/62
11/24/62
12/20/52
07/13/62
07/13/52
C7/ 13/82
08/06/92
08/13/52
08/10/22
06/12/82
06/12/92
06/12/92
06/25/32
08/3 1/82
09/:i/32
C5/:2/52
OS. 'OS/32
os/:s/82
05/23/52
09/23/52
05/23/52
09/23/52
j 9 . 2 3 1 £ £
05/23/52
(continued)
Plot
No.
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
S
6
c
6
S
5
6
6
5
6
6
6
6
5
5
5
c
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
c
i
Nominal
Loading
Rate
(%)
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13 '
13
13
13
13
10
10
10
10
10
10
10
10
1C
io
10
10
10
10
10
1 0
10
r
u
r.
- '
Rate
of
Sampling* Erais.
Status
BETfl
BETR
RR2
1.5HRP.T
BETR
BETP
.SHfl RT
1.5HR R
BETS
1.5 RT
RP.'
IRT.flfl
BETP
BETR
BETP
IRT.BR
BETR
IfiT.BR
RP-,
1ST. PR
BE-P
BETP
BETR
Bfl.PT
BT
BR
RT
IPP.BT
IP.T,flfi
BETS
BETR
BT
BT
RT.BP
RR
IRT.Rfl
BT
BT
6R
RT.BR
RR
BT.8S.
BT.BR
IflT.Bfl
BT.BR
IRP
IfiT.flfl
BT
BT
IRT.BR
1ST
BT
IST.BR
BT.BR
IP.T.Bfl
IPS.E7
IOT.PP
2 ~ "
4rf Pfi
(g/hr)
11.70
1 1 .70
35.89
21.45
6.82
6.82
.18.28
15.67
6.65
17.55
35.10
4C.22
15.63
13. 16
10.24
13.15
9.51
13. 16
356.90
115.95
45.67
24.82
14.62
39.49
1 1.70
10.23
34.59
3c7.83
401.30
64.56
29.55
23. '40
11.70
13.65
65.90
54.59
5.85
3.90
4.39
11.70
58.51
5.85
4.39
11.70
5.12
66.55
38.39
7.80
5.65
23.15
17.55
5.85
14.63
5.65
12.40
453i4C
235. 12
173. 4C
Vola. Soil
of Mois.
Slud. Cont.
(%) (%)
16
8
23
20
19
18
17
8
14 22
22
13
! 28
28
o
18
9
20
! :o
is
< '
4
9
5
o
7
4
1
5
5
7
1
:
7
Soil
Temp.
(°F)
106
6T
-
69
69
92
85
54
94
86
65
62
62
86
67
86
88
80
81
80
60
80
65
66
65
70
55
65
go
69
59
62
6 =
50
53
52
50
44
40
95
55
10s
95
97
97
102
102
95
97
56
63
60
95
63
55
72
^ . .
74
Rela.
Humid
(%)
68
72
71
39
31
si
31
52
53
60
60
g i
U 1
62
45
52
35
. 37
g 1
D
81
81
60
O U
56
56
6u
w U
62
11
85
75
78
80
60
65
86
85
W J
So
43
60
60
C3
D C
23
62
69
63
64
54
35
36
45
67
38
72
40
4 :
67
65
Reproduced from
o-c' best available copy. ^$^
-------
TABLE B.I.
(continued)
Date
of Plot
Nominal Rate Vola. Soil
Loading of of Mois. Soil
Rate Sampling* Emis. Slud. Cont. Temp.
Sampling No. (%)
09/2^/82
OS/26/82
10/C7/52
10/07/52
10/12/62
10/12/82
10/21/62
10/21/82
10/25/82
1 1/02/62
1 1/02/62
11/02/32
11/02/82
11/02/82
1 1/02/82
11/03/62
11/05/82
1 1/09/82
11/09/32
11/17/62
11/17/32
11/17/52
1 1/17/82
1 1/17/62
11/18/82
11/24/62
12/20/32
07/20/52
07/20/82
C7/2C/82
06/05/82
C6/C-5/62
08/10/52
08/10/92
08/P/62
08/17/62
C8/P/S2
08/17/32
08/25/32
08/31/62
09/01/62
09/02/92
09/05/82
03/23/32
09/23/52
09/23/52
10/07/62
1 0/C7/ :2
10/12/52
10/12/62
10/21/32
10/21/82
10/25/52
1 1/C2/62
H/C9/32
; 1 / ! 7 / 6 2
1 1 / ^ / 9 2
i / 7/ z~c
\\'.> 7/52 '
5
5
5
5
5
5
5
5
c
5
c
5
5
5
5
5
5
5
5
5
5
c
5
5
5
5
5
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
"^
10
10
10
10
10
10
10
10
10
10
r>
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
6
6
5
6
6
6
6
6
6
- 6
6
6
6
6
6
5
6
6
6
5
6
6
6
6
6
6
6
6
6
6
5
Status
BETR
BE'S
BT
1RT.BR
BT.BP
1RT.PR
BT.BP
1RT.BR
BT.BR
BT.9P
RT.5R
5RP.BT
SORT
2nR PT
4HR RT
BETP
BETS
BT.BR
IPT.BR
B:
PT.BR
IRT.RP
2HR S =
4riR fin
BETR
BT.BP
BT.BR
BT.BP
Iflfi.ST
IRT.RP
BT.SR
BT!BR
30RT.BR
BT.BP
RT.Bfl
RR
IPT.fiR
BT.BR
BT.BR
RT.BS
30PT.BR
180RT
BR
PR
IRR.RT
BR
1RT.BR
BT.BP
IRT.Pfl
BT.BP
RT.BR
B'.BR
BT.9R
BT.BP
BT.3P
PT.SP
Pc 'T
50=". PR
(g/hr) (%) U) t"FJ
61.24 . 70
31.17
17.55
61.43 . 16
11.70
175.51 13
16. OS
51.19
15.95
16.09
23. 6,
248.64 13
162.35
107.12
71.29
45.21
27.89
16.09
24.13
10.01
32.99
101.74 12
63.21
14!96 !
6.83
3.90
3.22
60.24
53.24
5.85
5.85
3.50
7.80 . 20
3.90
7.80
27.30 8
19.53 . 19
5.55
5.95
23.40
17.55
13.16 . 6
5.95
350.09 14
395.95
11.85
17.55 . 14
5.65
1170.07 14
11.70
36.55
7.31
4.33
4.33
4.33 . . 15
15.15 . 15
67.10 3
75
84
2 91
90
91
73
73
64
66
67
67
75
75
75
76
73
69
69
64
64
64
65
65
53
45
<; i
73
85
88
107
96
96
7 57
60
ec
62
4 85
67
69
90
96
9 65
72
72
72
62
3 82
73
74
62
53
62
5 =
65
7 =:
7 47
5C
22.14 . 5C
Re la.
Humid.
(%)
58
55
59
59
62
37
61
3^
4E
45
79
55
64
64
70
71
65
63
66
66
92
85
85
72
43
31
44
37
40
25
24
58
60
50
50
54
74
33
31
26
51
58
51
51
51
55
55
59
59
33
S3
37
37
39
63
£5
33
55
(continued)
Reproduced from
best available copy.
-------
TABLE B.I. (continued)
Date
of
Sampling
11/24/82
12/20/82
07/13/82
07/13/82
07/13/62
08/OS/82
06/10/82
06/13/52
08/13/82
08/2S/62
09/31/82
09/09/52
09/09/82
09/23/82
09/23/52
09/23/82
10/07/82
10/07/82
10/12/82
10/12/82
10/12/62
10/21/82
10/22/62
10/26/82
11/02/52
11/02/82
11/02/82
11/02/82
11/09/82
11/03/82
11/17/82
11/17/82
11/17/82
11/24/82
12/20/82
Plot
No.
7
7
4
4
4
4
4
4
4
lj
ij
4
14
4
4
14
4
4
4
4
4
4
4
14
4
4
4
4
4
4
4
4
4
4
4
Nominal
Loading
Rate
6
6
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
^
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Rate
of
Sampling*Emis.
Status (g/hr)
BT.8R
BT.Bfl
BT.Bfi
Rfl
1RT
B~ Bfl
RT.Bfi
Rfl.ET
RT.flfl
BT.Bfi
BT.BS
BT.Bfl
20flT,Bfi
BT.Bfl
RT.BR
RT.fifl
BT.Bfl
RT.BR
BT.Bfi
80=3
RT.flfl
RT.Bfl
BT.Bfl
BT.Bfl
' BT.BP
RT.Bfl
ISSfl.BT
35flT.RR
BT.Bfl
RT.BR
BT.Bfl
RT.BR
RT.flfl
BT.BP
BT.Bfl
5. 5
2.93
3.22
35.57
24.57
5.85
14.52
42.90
30.22
2.92
2.92
2.92
14.62
3.80
12.54
190.11
5.85
16. C9
4.39
116.99
51.18
21.20
13.16
4.39
4.39
12.54
233.98
145.09
8. 65
15.15
5.85
12.99
32.48
5.85
2.93
Vola. Soil
of Mois. Soil
Slud. Cont. Temp.
43
1
27
3
17
6
13
13
11
14
U
14
14
14
14
14
14
13
13
13
13
13
13 13
9
9
9
53
S3
S3
SO
0 £9
62
0 63
87
£7
7S
3 e:
4 7]
9 71
7;
76
5 75
6 =
72
B'J
6!
57
59
C-
61
6 =
gc
6 =
3 49
z *
43
52
Rela.
Humid.
43
2t
5:
5r
55
23
'r-i
62
w ''
2?
27
3
£ Z
4C
42
63
. 53
52
43
65
§3
;;
5:
= 2
ct
73
7-
7C
76
71
62
6£
14:
29
k AT = After Tilling, AA = After Application,
IAT = Immediately After Tilling, BT - Before Tilling,
BETA = Between Two Application, BA = Before Application,
20 AT = 20 Min. After Tilling, 90 AT - 90 Min. After Tilling,
2 HR AA = 2 Hours After Application
277
-------
TABLE B.2.
CALCULATED EMISSION RATES OF TOTAL
VOLATILE HYDROCARBONS FOR LABORATORY
EXPERIMENTS
Date
of
Sampling
06/31/83
06/01/83
06/01/83
05/01/83
06/01/63
06/01/63
06/02/63
06/03/83
05/23/33
06/04/83
05/05/93
06/08/83
06/C8/S3
06/05/33
06/0:/83
06/01/33
06/01/63
06/01/63
06/01/63
06/01/83
06/01/83
06/C1/83
06/02/83
06/03/63
06/03/83
06/04/83
06/08/83
05/08/63
06/09/83
06/03/83
OS/03/83
06/03/63
06/03/83
05/03/83
06/C3/63
05/03/83
08/04/83
06/08/93
06/06/83
06/05/63
Co/:C/53
05/10/83
05/10/93
05/11/83
05/16/33
05/16/93
05/15/33
05/16/83
05/16/83
C5/16/93
05/15/83
CS/15/63
05/16/93
05/15/63
05/17/63
Cs/'-S/S;
C 5/26/55
0:.' '. 2/B3
05/ir/53
(continued)
Time
Since
Appl.
(hr.)
0.033
0.055
0.083
0.166
0.750
3.200
24. COG
48.000
48. EGO
72.000
96.000
163.000
166. SCO
192.000
0.033
0.066
0.168
0.415
0.750
1.330
3.500
4.250
24.000
46. COO
48.50C
72.022
158.000
168.500
192.000
0.033
0.066
0.165
1.000
1.500
3.000
6.500
24.000
120.000
123.500
144.000
'66 3011
169.500
172.000
132.000
0.033
0.368
0.165
0.330
0.500
0.666
3.633
1 . 300
3.000
5.QOO
24.320
*!'!?
4s. "wC
Loading
Rate
Rate
Soil Vola.
of Soil Rela. Mois. of
Emission Temp. Humid. Cont. Slud.
(%) (g/hr) (°F) (%) (%) (%)
3
3
3
3
3
3
' ' 3
3
3
3
3
3
a
3
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
511.906 65
477.778 85
392.461 65
341.270 65
136.506 65
59.722 65
25.595' 85
23.595 85
58.0:3 65
13.650 65
12.790 85
12.790 65
42.558 85
14.620 65
546.033 65
546.033 65
392.450 65
238.889 85
170.638 65
136.503 85
76.785 85
66.254 65
28.154 85
25.595 85
63.135 85
23.875 85
21.933 85
46.315 85
30.710 65
590.150 65
580.150 65
460.715 65
307.143 65
255.953 65
153.570 65
110.913 65
42.657 65
28.030 85
59.722 65
24.161 65
14.525 85
43.721 65
32.215 85
15.720 65
307.144 60
3C7.144 60
255.953 60
213.294 60
187.895 60
170.635 60
153.571 60
153.571 60
61.428 60
37.539 60
16.759 60
5.21C 6C
32.420 60
3C.719 5C
15.357 60
278
52 12 6.5
52 12 8.5
52 12 8.5
52 12 8.5
52 12 8.5
52 12 8.5
52 12 8.5
52 12 6.5
52 12 8.5
52 12 8.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 8.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 8.5
52 12 8.5
52 12 9.5
52 12 8.5
52 12 8.5
52 12 6.5
52 12 3.5
52 12 8.5
52 12 6.5
52 12 8.5
52 12 6.5
52 12 8.5
52 12 8.5
52 12 8.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 3.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 8.5
52 12 8.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 6.5
52 12 3.5
52 12 8.5
52 12 3.5
52 12 6.5
52 12 9.5
52 12 6.5
52 12 8.5
-^ 12 =.5
52 12 8.5
EZ 12 =.5
52 12 S.5
Reproduced from
best available copy.
-------
TABLE B.2 (continued)
Date
of
Sampling
05/20/83
05/20/93
05/20/83
C5/20/83
05/21/83
05/22/63
05/17/83
05/17/8-
05/17/63
05/17/63
05/17/53
05/17/83
05/17/83
05/17/63
05/17/83
05/17/83
05/16/83
05/18/63
05/19/53
05/19/83
05/1S/63
05/19/63
05/20/53
05/21/83
05/21/83
05/22/63
05/23/83
05/24/83
05/214/83
05/24/63
05/24/83
05/24/83
05/24/53
05/24/63
05/24/63
05/24/83
05/25/83
05/25/63
05/25/63
05/2S/63
CE/26/S3
05/26/63
05/27/53
05/29/53
05/25/93
05/29/83
05/30/63
03/31/65
C3/31/83
03/31/63
03/31/63
03/31/63
03/31/63
03/31/63
04/01/63
0!,/32/S3
C^-'-'i'z'-'
±->'~3/*l
04/33/83
(continued)
Time
Since
Appl.
(hr.)
96.000
96. 5CC
96.000
101.000
120.300
144.000
0.033
0.066
0.166
0.333
0.50C
0.750
0.833
l.OOC
4.000
6.000
22.000
24.000
46.000
48.500
49.010
53.000
72. COO
96.000
96.500
120. COO
144.000
0.033
0.166
0.333
0.500
0.750
1.000
1.750
4.000
5.000
21.000
24.000
48. COO
46.500
4S.012
54.000
72.000
9S.COO
So. SCO
120. SCO
144. COO
O.C33
0.063
1 . CC3
2. COO
4.0GC
e.crc
e.coo
2".. 000
is.QC'O
^ ^ *. - "
* k '« -
74.C-::
Loading
Rate
(%)
3
3
3
3
3
3
6
6
6
6
6
6
'6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
10
10
10
10
10
10
10
:o
1C
10
10
1C
10
10
10
10
10
1C
10
10
3
3
3
3
3
3
3
3
3
3
3
2
Rate
of
Emission
(g/hr)
1C. 238
23.666
14.504
14.504
10.236
7.676
375.397
341.270
255.953
221.626
2C4.762
196.230
167.698
162.103
59.722
37.500
25.595
20.476
20.476
54.603
51.190
34.127
20.476
11.944
32.420
13.550
8.531
375.394
307.143
273.016
255.953
236.889
230.357
213.294
170.535
133.095
29.008
27.613
25. 446
66.730
61. 93'4
3C.714
23.868
11.544
47.777
13.650
11.051
204.752
170.635
127.976
119.444
40.952
22.761
2S.C08
13.650
5.572
22. 192
13.550
11.344
Soil
Temp.
(°F)
60
60
60
60
60
60
60
60
60
6C
60
60
60
60
60
60
60
60
60
60
60
60
60
6C
60
60
60
50
60
60
60
60
6C
60
60
60
60
60
60
60
60
60
60
6C
60
53
60
35
35
35
35
35
35
35
35
35
35
35
35
Rela.
Humid.
(X)
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
55
52
52
r:
Soil
Mois.
Cont.
00
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
:2
12
12
12
12
12
12
12
12
12
12
12
12
:2
Vola.
of
Slud.
(X)
6.5
8.5
8.5
6.5
6.5
8.5
6.5
6.5
8.5
6.5
8.5
6.5
6.5
6.5
6.5
8.5
6.5
6.5
6.5
8.5
8.5
8.5
6.5
6.5
8.5
6.5
8.5
6.5
6.5
6.5
8.5
8.5
8.5
8.5
8.5
6.5
6.5
6.5
6.5
6.5
8.5
6.5
S.5
6.5
6.5
6.5
6.5
6.5
6.5
8.5
8.5
8.5
8.5
8.5
6.5
8.5
8.5
6.5
6.5
279
.
available copy,
-------
TABLE B.2. (continued)
Date
of
Sampling
04/03/83
04/04/83
04/04/83
04/04/83
04/04/83
04/05/83
04/06/83
04/04/63
04/04/83
04/04/83
04/C4/83
04/04/63
C4/04/63
04/04/63
04/04/83
04/05/83
04/06/63
04/06/83
04/07/63
04/08/63
04/08/83
04/05/53
04/10/63
04/01/83
04/01/83
04/01/83
04/01/93
04/01/63
04/01/83
04/02/83
04/03/83
04/03/83
C4/04'93
04/05/83
04/05/63
04/06/83
04/07/53
OS/10/63
C6/1C/33
CS/10/63
OS/10/83
25/JO/83
03/10/83
05/10/63
C6/10/83
06/10/83
05/12/83
06/12/83
?6/ 13/83
05/14/63
05/:4/83
06/15/53
06/16/83
C7/D5/63
07/C5/c:
37/Cs/s;
07/C-5/C?
C7/C5/32
C7/C5/S3
(continued)
Time
Since
Appl.
(hr.)
78.000
So. COO
95.500
99.000
101.000
120.000
144.000
0.033
0.165
0.500
0.750
2.000
4.000
6. 000
6.000
24.000
48.000
48.500
72.000
96.000
96.500
120.000
144.000
0.033
0.083
0.50C
1.000
5.000
B.COO
24.000
48.000
48.500
72.000
96.000
96.500
120.000
144.000
0.033
C.C6S
0.266
C.25C
1.000
2.000
4.000
6.000
24.000
49. DOG
43.500
72.000
S6.00G
95.500
lic.oao
144. 003
O.C35
0.083
0.:35
0.333
i " c "
3. COS
Loading
Rate
(%)
3
3
3
3
3
3
3
6
6
6
6
6
e
6
6
6
6
6
6
E
6
6
6
10
10
1C
10
10
10
10
10
10
10
10
10
10
10
6
6
6
6
6
6
6
6
6
6
6
5
6
5
6
6
6
6
6
6
S
6
«
Rate
of
Emission
(g/hr)
11.944
8.531
20.476
15.357
11.944
8.531
5.972
307.143
238.889
187.698
153.571
136.508
54.603
42.656
23.888
17.063
10.238
35.833
12.797
10.236
34.127
6.625
5.119
236.889
204.762
170.635
127.979
40.952
34.127
22.182
11.944
39.246
13.650
11.944
35.833
10.238
8.531
511.905
477.779
375.397
307.143
280.083
240.550
204.782
127.979
54.603
40.952
64.841
37.539
34.127
50.337
34.127
30.7m
34':. 270
290.080
204. 76C
170.530
i2,.=s;
30. 710
'80
Soil
Temp.
(°F)
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
35
60
60
60
50
60
60
60
60
60
50
50
50
60
60
60
£0
60
SO
60
50
SO
50
Rela.
Humid
(Z)
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
52
75
75
75
75
7 =
75
Soil
Hois.
. Cont .
(%)
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
12
12
12
12
* u
12
Vola.
of
Slud.
(%)
8.5
8.5
8.5
8.5
8.5
6.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
6.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
6.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
6.5
8.5
6.5
8.5
8.5
8.5
8.5
6.5
8.5
8.5
8.5
6.5
8.5
8.5
e c
s'.l
e.=
c s
e!§
Reproduced from $%
best available copy.
-------
TABLE B.2. (continued)
Date
of
Sampling
07/05/83
07/06/33
07/07/83
07/07/63
07/08/83
07/09/83
07/09/63
07/10/93
07/11/53
07/05/63
07/05/53
07/05/63
07/05/63
07/05/53
07/05/83
07/05/83
07/05/83
07/07/63
07/07/83
07/08/63
07/09/83
07/09/83
07/10/83
07/11/63
Time
Since
Appl.
(hr.)
5.000
24.000
46.000
48.500
72.000
96.000
95. SCO
120. OCC
145.000
0.033
0.16E
0.333
0.5CO
1.000
4.000
6.000
24.000
46.000
48.500
72.000
95.000
96.500
120.000
IMS. 000
Loading
Rate
(%)
6
6
6
6
6
6
6
6
E
10
10
10
10
10
10
10
10
10
1C
10
10
10
10
10
Rate
of
Emission
(g/hr)
27.330
15.350
10.230
19.520
10.230
6.820
14.500
8.530
5. 110
341.270
238. SSC
204.760
1=5.23:
153.570
93.940
76.780
18.760
14.500
23.38:'
15.350
10.230
20.47Q
1 1.940
8.530
Soil
Temp.
(°F)
60
60
60
6C
60
60
6C
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
Rela.
Humid.
(%)
75
75
75
75
75
75
75
75
75
75
7^
75
75
75
75
75
75
75
75
75
75
75
75
75
Soil
Mois.
Cont.
(%)
1 1
\\
\\
le
12
1 £
12
2 2
i g
Is
\ *
<2
12
> ;
;2
\ ?
j ^
;2
12
12
^ £
12 '
12
Vola.
of
Slud.
(%)
6 5
6.5
g =
6.5
c 5
6.5
6.5
6.5
6. 5
6.5
c . 5
c | 5
£ t -
6.5
6. 5
6 . 5
£ . ~
6.5
6. 5
8.5
6. 5
6.5
e c
6.5
* Soil and sludge mixture was tilled.
281
Reproduced from
best available copy.
-------
TABLE B.3. THE TOTAL VOLATILE EMISSION MODELS FOR FIELD DATA
to
00
1. Model 1
Time <10 hours
Dependent Variable: Emission
R2 = .83 ,
Independent
Variables
Intercept
Soil Temperature
Moisture Content
Time Since
Application
Loading Rate
Relative Humidity
2. Model 2
F Value =
Estimate
76.594
.769
8.828
-20.645
9.985
-2.025
Time <10 hours
Dependent Variable: Emission
R2 = .76 ,
Intercept
Soil Temperature
Moisture Control
Time Since
Application
Loading Rate
Relative Humidity
F Value =
.184
.268
1.879
-.084
.931
-.371
Rate
27.49
T for Ho:
Independent
Variables = 0
1.48
1.77
5.08
-7.35
4.31
-2.81
Rate
49.83
.04
8.18
9.67
-7.15
4.51
-5.26
Probability
|t| Cal.> |t|tab.*
.1508
.0874
.0001
.0001
.0002
.0090
.9716
.0001
.0001
.0001
.0001
.0001
' .
Standard
Error of
Estimate
51.849
.434
1.737
2.810
2.316
.721
5.163
.032
.194
.011
.206
.070
* Ho is rejected if the probability [~t~| cal.>
-------
TABLE B.4. EMISSION RATES OF MEASURED HYDROCARBONS
to
00
U)
Temp = 85, Loading Rate = 3%
TINE SINCE RPPL. IHOUNSI
COMPOUND NRME
PEHTRNE
CTCLOPENTRNE
HEXflNE
MEIHTl CTCLOPEN1RNE
BEN/fNE
2.M-C1INETHUPENIRNE
CTCIOHf IHNE
3-MEIHTLMEIRNE
ME 1HILITUOHI XRNE
2.5-OIHE1HTIHEIRNE
2.3.M-IHIME1HTLPIN1RNE
3-NEIHHHfPIHNE
2.?.S-IRI«EIHII Ht«ONE
. l.q-OHtllHHOfN/m
SUM OF IM COMPOUNDS
101(11 VOIfll. RS HFXRNE
X IM COHP/IOIHL VOIIII
.033
0.1416
0.916
6.878
3.59M
2.6
16.7
U. 2 72
8.839
7i8/l
33.018
7.218
M . GH 7
5.326
ini.SfU
M/7. 7/9
22.l
'11 1 .
-------
TABLE B.5. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
to
03
Temp. = 85, Loading Rate » 6%
tine SINCE RPPI. IHOURSI
CONFOUND NRNE
. PENTRHE
.C1CIOPENIRNE
. NEXRNE
. ME1HTI CTCLOPEN1RNE
.BEN.'ENt
. 7.M-.1NEIHTIPENIRNE
.CKLOHURNC
. 3-MEIH1IHEIRNE
. HEIHHCTU OHtXflNE
0. 2.5-OINEIHHMH.flNI
1.2.3.4 IRINtlHUPlNIRNE
. 3-MEIIUI HirillNE
3. 2.2.S- IHIHI IMTlHtXrtNE
». I.U-Olm IHTLuiNMNt
SIIH Ot 14 C.IM»1OllNnr.
tOlfll VfllRI. RS NIIRNE
7. iv coKp/ioini vniRi
.033
0.382
0.402
8.848
4.42
2.694
20.156
5.3B8
10.002
9i«UU
J4.9G8
6. IU4
4.49
4.UH
I??. 176
540.0110
.166
0.342
0.46
7.419
3. KG
2 45
20.085
4.V08
9.711
I..7I.1
9. 145
3 1 't(ir
e.G)6'
4.304
'1. MB
li'i.niu
1!.'
1 IS.'.UB
27. 4G
S
IOUH / 1
6.04
0.3IM
0. I6B
U.20V
I.BG
0*21
1.1)4
O.SI4
1.448
3. '.'.4
I.6S
1. 19
P . U24
I'l.n'.n
l'>4 . 2R4
i \ . i n
24
80 SQ.fl
6.05H
O.IB36
II. 135
O.llil
0. 197
O.U8B
0.3919
0.128
0.264
1.4 IB
0.3/6
0. JR)
1 . 1i| |
!>. IMH
2H. I!i4
IH.29
48
. IPLOI
(
6.021
0.018
0.1021
0.09
0.104
0.0'jl
0.4)9
0.0)4
0. I'JH
0.324
O.IG9
0* 1*3
0.iS2
2.412
2S.S98
9. '12
48.5"
RRERI
0.022
1.34
0.08
0.098
0.742
0. 194
0.098
0.2GB
H.0'10
O.dlib
I.I 14
0. 'j*J4
O.HS
2.SI6
I.RBO
61. 115
IS. (.4
168
0.040S
O.'JUb
0.017
0.26
0.372
0.0.18
O.OtiB
0.042
0.01)5
0.091
U.IS
0.331
O.J4S
0 . 4 VI
3.07M
2I.9IH
II.O'I
IGB.5"
O.UJS
0.946
0.113
0.3B2
O.S2
O.OS2
0.193
O.OB3
O.OM7
0.0'IS
O.M'i
I.OR2
0.6MG
i.n^a
G. it 12
46.415
I4..'!l
192
0.006
0.172
0.02
0.048
O.OH4
0.046
0.02
0.04
0.028
0.81
0.18
0. 124
O.IIGB
O.S02
2 . H/n
3u. no
9.2U
SOIL flNf) SLUnGE MIXTURE Hqs llllfD
-------
TABLE B.6. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
ro
CO
U1
tint SINCE RPPI. IHOURSI
CONFOUND NflHE
. PENIRNE
. CtClOPENtflNE
.HE JAKE
. HETHTl CTCIOPENIRNE
. BIN/INF
. 2.4-OINFIHHPENIflNE
. C1UOHIIHNE
. 3-HEIHUH[IANE
. HE hmr.Tr.imif >BNF
. 2.S-OIMI iHUHltDNt
1. 2.3.4-iniMriHHPINIRNE
I. 3-Nf IH1LMEPIRNE
j. 7.2.5-llllMf IHllHflflNE
4. 1.4-OlrttlMliniN/INE
sun or IM coHi'numis
10 Ifll VOIIII. IIS Ml IHNC
* IM COMP/IOlnivai
Tui.lg
.166
= 85,
1.0
Loading
a.
CRflNS
0.3911
0.404
8.198
3.88
?.»5
21. W
3.116
II 658
9.33
I 3. 284
^ 6M7
l.H
8. b3b
IM7.7.8B
. 4f.ll. ll'j
31.17
0.166
1.069
2.B55
2.355
1.67
9.017
2. 8tf5
S . 779
3. KiM
5. 6119
77. 11
S.M9b
3. dSM
5.BSM
i? nsi
30). 143
73. If
0.
0.
n.
0.
u.
3.
0.
i.
2t
7.
3.
7.
i| ,
(>fl
II
0
74
/ HOHR / 180
006
639
88
7Sb
8/2
IOM
173
98
I«'G
IM4
078
no
5(1?
016
11.913
0.03
O.S7?
0.07
0.844
1.212
0. 716
0. I97
O.MIIM
0! MM
7.I4U
0.90?
O.O.1
1.097
IO.MJ1
Mc'.GSB
?'..MO
Rate
96
SO.FI.
0.026
0.423
0.079
0.44
0.711
0.196
0.096
0.139
0.571
0.77
O.S9I
0.492
0.521
0.877
5. 7H7
76. II'IC
18. BU
= 10%
9G
.5-
192
216
(PLOt RflfRI
0.
o!
0.
1.
0.
0.
0.
0.
0.
1.
0.
1 .
2.
II
59
in
036
793
084
816
736
3
109
187
GI4
964
286
919
306
187
..117
. /?7
.97
0.022
0.22
0.064
0.074
0.144
O.OtlM
0.032
0.3
0.074
0.816
O.MI4
I.M.'G
1 . 0PM
I.5G
R.3MM
7M.Hit
70.7(i
0.
6.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
3.
IM
77
03?
02B
01
054
OUB
71?
OOR
274
2/4
IS8
S37
19
3 JO
. 0.'5
. II
son RNO siuur.t nmimr MUS TMKO
-------
TABLE B.7. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CI1ROMATOGRAPHY
oo
o
Temp » 60, Loading Rate = 3%
111, "*CE BPPl. IHOURSI
CONPOUNO NRNE
I.PENTRNE
J.CTClOPENtflHE
« HtlBNF
4. METHH CTCLOPEN1RNE
t BENtlNE
('. 2.4-OINEtHTlPENIRNE
r.ClCLDHLINNC
I.3-HEIHUHEIRNE
10. 2.S-DIHUHHMEIONE
U.2.3.4 iniMUHlLPINIflHt
12. 3-MEIHHMEPIRNE
|»! 1.4-OINI IHUBIN/INI
lOIHI VOtRI. HS HI IRNE
AliWINr, Minn -jNlflin
X 14 IOMP/IOISI ynifil
.033
0.026
0.082
3.766
2.7R2
1.248
2.476
1.088
7.60
S.002
3,202
I.S36
1.51G
3. GO
Ml.. I'jfi
1117. 144
IS. Ill
1.0
0.088
0.356
0.6S 1
\ .624
I.It
2.0R2
2.SI6
2. I»M 2
9.4114
1 . 208
1 . II 1 1
2.187
3 I.I OH
IM.S/I
3.0
0.00fl2
0 102
0.43G
0. J.4
0.3HH
1.702
0.3.1^
ri.HM2
ii. nun
0.14
3.H'.?
O.IISG
0. /'.B
ll.fl'M,
11.1114
Gl . 4<*tf
n.;,i
24
CURBS /
n.nns
0. 104
o.nu;
0.3
0.328
O.OG9
tl.06
n.092
n.4 .
U. I'j?
0.612
II. 762
ll.4Gr.2
.1. !IS!t
iu. ;r>9
1 /.OH
MB
HOUR /
0.003
n.iiG
0.1106
0.048
O.U74
O.OS7
O.OIS
O.OS7
II.OGU
0.102
0.21
0.128
0.100
0.1114
I./40
S.2IO
21. MO
48.5-
ISO SO.
0.019
0.032
0.28
0.246
0. J78
O.Of.8
0.268
0.312
0.2S2
O.S92
1. 108
0.7'jG
P. 708
I.S2
12.420
20.2)
tt
F1. IPLOI
O.OOSI
O.OS7
0.019
0.17?
0.102
O.OM8
0.022
II. IS6
o.ma
U.2G2
O.S07
0.414
0.3.S
1.291
3. e»2n
IS.1S7
^.J2
96
RREftl
0.004
0.2
0.008
0.148
0.09}
O.C2S
0.008
o.usa
O.I
O.Ofi
0.121
0. I>i2
0. 122
0.32
1.409
10.218
13. 7G
96.5.
0.03?
0.41
0.036
0.326
0 ''1
O.QG2
0.014
O.ISG
0.464
0.2
0.268
0.488
0. 3GR
O.S98
3. fl7^
23.818
16.24
09
0.007
0.298
0.008
0.126
0.127
0.02
0.0/2
o.or.G
O.IV
0.43'i
0.126
0.149
0.167
0.47?
2. 1 74
1 4 . S04
14. 'J9
IB8
0.002
o.osa
0.001
0.018
0.02%
0.004
O.OOG
0.017
0.024
0.138
0.018
0.141
0.'J9'I
O.llb
O.C>fi2
7.6/8
8.G2
SOU UNO SlUOlU NIIHIRE MRS llli.10
-------
to
00
-J
TABLE B.8. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp =60, Loading Rate - 6%
TINE SINCE flPPL. IHQURSI
COHPOUHO NBHE
,
t
f
t
4
f
»'.
i.
i.
j.
i.
PENTRNE
CTCIOPCNIRNE
HEIRNt
KEIHtl CTClOPENtRNE
BENZINE
2.4-OIHE1HUPCNTflNE
CTCLOHEXRNE
3-HEIH1LHEIRNE
HEIHHCUIOHEKRNF
2.S-OINEIHUHEXRNE
2.3.4-lHIHFtMHPEMI:>e
3-«IHtlHCPIRNF
2.2.5-IIIIHC IIUIHEIflNt
1.4-OINEIHUHrN/tNF
SUN m 14 COMPOUNDS
»S5iit VOLRT. RS htlRNE
'/. IM COMP/101HL VCini
.033
0.313
0.301
S.67?
q.???
?.8M?
13.132
1.69?
7.198
6.791
S.69C
26.GS
3.098
M.3m
3. J36
06. SG?
3MI.170
?S.36
6.0
0.0?M
0.79V
0.428
0.36
U.32
?.o?
0.3M2
0.9GS
O.SG4
O.S99
3.33
0.788
1.318
I.I/?
12. /?M
37.110
33.9?
?M M6 48. S" 72 96 96.5"
CRRKS / HOUR / ISO SO. Fl. IPI.OT RRERI
0.0041
0.109
0.037
O.I/I
0.?97
(1.3'I9
0.137
0.3S9
O.MIIS
0.?9?
U.7?9
O.M8
,
0.5)9
3.9RR
20. >«)6
19.48
0.007
0.08S
0.018
0.085
O.I'J'I
n.?36
0.026
0.104
0. 13")
O.?ti
0.63?
0.333
0.2?G
0.4?)
?.7?5
20.376
13.3)
0.022
O.T4
0.298
0.122
U.2B4
O.S96
0.235
0.309
0.253
0.601
1.897
0.73
0.7GI
1. IBB
7.526
54.603
IJ.78
0.016
O.I2S
0.070
0.094
0.109
0.2?
0.086
0.169
0.131
0.2?S
0.6?6
0.4J6
0.450
0.544
3.31)
20.476
IG.?0
0.004
0.189
0.023
0.0/7
0.104
0.074
0.014
0.072
0.099
0.112
O.I8G
0.12
0.248
0.24
1.61?
11.944
13. SO
0.01
0.288
0.05
0.086
0.20V
0.184
0.024
0.117
0.136
0.251
0.521
0.41
0.428
O.r>55
3.3G?
32.U20
10.37
120
0.006
0.162
O.U6S
0.054
0.072
0.0/6
0.014
0.104
0.068
O.I?
11.086
0.208
0. II
0. Jf,
I.S'li
13.650
11.3?
146
6.004
6.001
0.003
0.091
0.004
O.OS?
O.U<43
0.125
0.125
0.239
.
0.33
1 . 1) 1 7
8.S1I
1 1 . U?
SOU RNO SIUOGF HtllURt HRO 111.110
-------
TABLE B.9. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp =
1INE SINCE RPPL. IHOURSI
W COMPOUND NRHE
00 . ..... ---- _.
00 |. PEN1RNE
2. CICLOPENIRNE
]. HEXRNE
4. HEIHTL C1CLOPENTRNE
J. BENZENE
». 2.4-OIHETHTLPENIRNE
7. CTClOHEXflNE
|. 3-HEIHUHEXRNE
». ME1HHC1I lOHEXRNt
10. 2.5-DIMf IHUHlxflNE
It. 2.3.4-IMIHI IHHPCNinNE
It. 3-MI IHIIHIPIIINI.
11. 2.2.5-iniMfll(TlHrxflN£
£f~?
CD (D
"*" -!
38.
=8
5",
o
n X
0 3
3
lsj&5
14. I.4-OIME1HIIHINHNE
SUH Of 14 COMPOUNDS
10IRL VOlfll. RS HfXRNE
"I. 14 COHP/IOIHI vgifll
.033
0.252
0.296
6.09
6.648
1.042
15.47
4.014
7.388
6.9Sfi
6.204
28. 90
5.164
4.r,or,
9>. 786
307.143
31.64
.SO
0.126
0.189
3.384
1.538
I.44S
9.886
2.0J6
i'.til
I9;45
2i33S
4.141
0 1.450
304.016
20.21
60,
Loading Rate = 10%
1.0 4 24 48
r.nnMS / HOUR / too SO.M
0.098
0.308
2.281
1. 144
0.971
4.93B
1.644
2.975
2. 101
2 037
7.644
2.914
1 . .Ill'l
7.86
3J.I67
203.000
Ib. J4
0.01
0.7H6
2.431
0.37
0.41
3. OSS
0. S J5
I.S16
0.0 19
i. in
1 1 tV 9
?.UJ9
i . ? n
«* . i'fi 3
f\\ , (jug
170.635
14.09
0.006
0.2M
0.12
0. 161
0. J24
0.6
0.393
0.678
O.'j?
O.llHi
I.J»!i
D! /U4
O.HH1
6 . (IOH
77.HI3
?M . fl'l
0.002
0.205
0.041
0.096
3.196
0.271
0.035
0. 143
O.IM2
0.194
O.C9
0.227
0.369
O.S48
3. I'j9
26.448
1 1.94
48.5-
. IPL01
0.029
0.316
1.28
0.32
0.25
2.202
0.248
0.861
0.2(i
1.145
4.)
1.557
0.98
1.565
15.919
86.710
17.94
54
RRERl
0.006
0.139
0.098
0.242
0.0<,
0.328
0.142
0. 194
0.092
0. 702
1 fl'14
0./4I
0.78
0.8J4
S.4'l?
30.774
1 M,fl
72
0.017
0.11
0.072
0.095
0.113
0.281
6.141
0.066
0.712
O.CI I
0.364
0. 348
0.5'/
2.919
23.8i,8
12.56
96
0.007
0.325
O.OR4
0.016
0.041
0.208
0.013
0.102
0.049
O.<*09
D.I, 111
0.3(14
0.2SI
0.99
3.202
11.841
27.04
96. 5«
0.02
0.362
0.264
0.172
0.242
0.587
0.05
0.36
0.7QI
0.699
1.911
0.942
O.I,.".,
1.215
7.75,7
4>!.OIIO
I7.H2
,46
b"li<"i
o'.?i'i
0.012
0.707
0. 2i*4
0.091
o.o.i;
0. II',
O.i"li,
U.IMH
0. I'll,
0. J'lll
0.4 -I,
o.i.n.
l.^lc.
1 1 1,'tll
2.1. Mi
SOU RNII SLUDGE NIIIIHU MRS 1IUIO
-------
oo
vo
TABLE B.10. EMISSION RATES OP MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp = 35, Loading Rate = 3%
TIME SINCE flPPL.IHOURSl 2.0 6.0 48 48.?
COMPOUND NRME GRRMS / HOUR / 180 SQ.FT. IPI.UT
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
PENTHNE
CYCLOPENTRNE
HEXRNE
METHYL CYCLOPENTRNE
BENZENE
2.4-DIMETHTLPENTRNE
CYCLOHEXRNE
3-METHYI.HEXRNE
ME1HYLCYCLOHLXRNE
2,5-DIMF.lHYLHF.XRNE
2.3.4-TRIMnHTLPLNIflNE
3-METHTI HFPIHNE
2.2,5-TRIMF.THUHI:XMNE
1.4-DIMEHIYLHEN?l.Nfc
SUM OF 14 COMPUUNiJS
TOTRL VOLRT. RS HUXRNC
X 14 COMP/TOTRL VOLHT
0.
0.
0.
,
0.
*
.
0.
0.
0.
3.
0.
2.
1 .
1 1
11
9.
Ill
122
386
478
617
GflO
79?
3UJ
706
3?U)
2H7
.048
11.000
?8
0.
0.
0.
0.
0.
.
,
0.
0.
0.
0.
0.
1.
0.
LI .
32
13
035
1
on
147
132
173
152
If. 7
I UG
f j 'J
?fi
c* 1 4
3U
?70
. 182
..?3
SOIL RND SLUDGE MIXTURE MRS TILLED
-------
TABLE B.ll. EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
to
\o
o
Temp =35, Loading Rate = 6%
TIME SINCE RPPL. IHQIJR51
COMPOUND NRMi:
.50
CMRMG / HOUR / 190 SQ.FT. (PLOT RRFfU
1. PENTRNE
2.CYCIOPENTRNE
3. HEXRNE
A. METHYL CTCLOPENTRNE
5. BENZENE
6. 2.M-QIMETHYLPENfRNE
7.CTCLOHEXRNC
8. 3-METHTLHEXRNE
9. METHTLCYCLOHIXRNE
10. 2.5-OIMETHYLHF.XRNE
11.2.3.»4-THIMEIHU.PLNfRNE
12. 3-MCTHYI.HIP1RNE
13. 2.2.5-TFl!MCTIIYLHtXRNE
14. m-OIMETHYLHCNZENF
SUM OF 1M rCMPi.llIND1"'
TOTRL vnt.fli. nr> HFXRNE
'/. IM COMP/IHTHL VOI HI
n.?36
O.UR3
1.4-99
l.fl^B
1.S92
^j.3ll?
1.3M7
3.6^3
:i.ljj
?. 1
H.I, 48
P.901
2..'43
2.022
iG.rir.fi
I87.fi98
19. MR
O.OR5
0. IG7
o.oni
0. 125
0.210
0.20R
O.OM
0. 113
0.210
0. 107
O.DU1
0.229
0. KiO
0.3'.,b
2.679
10.23B
2i.i. 1 7
0.039
0. IfiS
0.007
0. 10
0. 10M
o.ng?
O.OMH
0.033
0.^1 /
OJJ9
O.IJ9M
(I.OR
n.071
0. J'J9
1 . 7R2
fi . 1 1 9
3M.M2
SOIL RNP SUIOGE MIXTIIPE Wfl5 TILLFO
-------
TABLE B.12,
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp. = 35, Loading Rate = 10%
to
TIME SINCE flPPL. (HOURS)
COMPOUND NOME
.033 4.0 7.0
GRRMS / HOUR / 180 SO.FT
24 48
(PLOT RRER)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
. PENTRNE
. CYCLOPENTRNE
. HEXRNE
. METHYL CYCLOPENTRNE
. BENZENE
. 2.4-DIMETHYLPENTRNE
. CYCLOHEXRNE
. 3-METHYLHEXRNE
. METHYLCYCLOHEXRNE
. 2.5-DIMETHYLHEXRNE
. 2.3.4-TRIMETHYLPENTRNE
. 3-METHYLHEPTRNE
. 2.2.5-TRIMETHYLHEXRNE
. 1.4-DIMETHYLBENZENE
SUM OF 14 COMPOUNDS
TOTRL VOLRT. RS HEXRNE
'/. 14 COMP/TOTRL VOLRT.
0.
0.
1.
^
0.
.
.
4.
3.
2.
8.
3.
3.
2.
32
134
581
723
61
742
803
573
759
005
305
9H8
.223
204.000
15
.80
0.
0.
0.
0.
0.
0.
0.
0.
0.
0,
1.
0.
0.
0.
7.
40
17
177
397
1 /I
198
699
722
235
381
861
466
123
465
509
958
362
.952
.98
0.056
0. 126
0. 122
0. 1 16
0.255
0.581
0. 147
0.282
0.398
0.274
0.03
0.292
0.253
0.53
4.361
34. 127
12.78
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
B
m
.
.
m
f
B
m
.
m
B
.
.
f
22
1
3
073
09
042
092
108
333
059
134
263
258
50'J
283
273
518
035
. 182
.68
0.
(1.
0.
0.
0.
0.
0.
0.
0.
Cl.
0.
0.
0.
0.
2.
1 1
23
065
122
07
07
102
245
022
122
263
248
433
31 1
243
504
8!8
.944
.59
* SOIL RND SLUDGE MIXTURE WRS TILLED
-------
TABLE B.13. EMISSION RATES OF MEASURED HYDROCARBONS
GAS CHROMATOGRAPHIC FIELD DATA
to
K)
Plot #4
8/10/82 8/13/82 10/7/82 10/12/82 11/24/82 5/9/83
AT AA AT,AA BT AT AT,AA BT BT AT
Pentane
Cyclopentane
Hexane
Methylcyclopentane
Benzene
2,4-Dimethylpentane
Cyclohexane
3-MethyIhexane
Methylcyclohexane
2,5-DimethyIhexane
2,3,4-Trimethylpentane
3-MethyIheptane
2,2,5-TrimethyIhexane
1,4-Dimethylbenzene
1.30
.721 6.010
1.242 6.24
+ + + -I- .702
3.521 2.748 1.460 1.264 2.296
.060 .093 1.617 .148 .108
.139 + + .392 1.377
.076 .513 1.729 .447 +
.108 .783 1.868 .579 .835
.089 .674 2.319 .544 .689
.118 1.524 2.293 1.235 1.480
.223 2.213 2.500 .521 1.739
.119 2.907 + .438 .902
.274 5.773 2.462 1.423 1.448
.109
.790
.159
1.900
2.229
.650
13.559
8.920
6.806
26.090
7.770
12.104
12.480
.802
.730
.150
2.100
.447
.598
.662
.882
1.000
.802
2.481
.026 .028
.012 .204
.054 .095
.061 .567
.087 .569
.079 .105
.048 .139
.068 .123
.128 .627
.132 .240
.122 .181
.156 .231
.161 .163
.096 .658
(continued)
-------
TABLE B.13. (continued)
to
VO
Plot # 5
10/7/82 10/12/82 11/24/82
BT AA AT,AA BA
Pentane + + +
Cyclopentane + + +
Hexane + + +
Methylcyclopentane + + +
Benzene + 2.879 2.345
2,4-Dimethylpentane + .195 .210
Cyclohexane .073 + +
3-Methylhexane .076 .955 1.041
Methylcyclohexane .061 .831 . 1.169
2,5-Dimethylhexane + .866 1.657
2,3,4-Trimethylpentane .112 3.486 3.040
3-Methylheptane .657 11.970 12.597
2,2,5-Trimethylhexane .183 + +
1,4-Dimethylbenzene .557 20.770 16.610
.032
.114
.044
.316
2.071
.343
.144
.187
1.118
.186
.288
.309
.208
.878
12/02/82
BT
.029
.113
.034
.277
1.534
.212
.140
.128
1.090
.104
.174
.131
.117
.408
5/9/83
BT AT
+ .044
+ .218
+ .023
.145 .570
.323 .707
.044 .190
.040 .123
.034 .134
.258 .679
.077 .223
.066 .165
.094 .425
+ .181
.190 .660
(continued)
-------
TABLE B.13. (continued)
to
Pentane
Cyclopentane
Hexane
Methylcyclopentane
Benzene
2,4-Dimethylpentane
Cyclohexane
3-Methylhexane
Methylcyclohexane
2 , 5-Dimethylhexane
2 , 3 , 4-Trimethy Ipentane
3 -Methy Iheptane
2,2, 5-Trimethylhexane
1 , 4-Dimethylbenzene
IAT
.004
.041
.034
.282
.289
.100
.094
.203
.289
.073
.193
.110
.075
.423
Plot # 7
5/9/83
30 min. AT
.065
.280
.023
.522
.508
.088
.129
.125
.616
.110
.211
.110
.065
.472
Plot #1 -. . . .
6/9/83
AT
.044
.285
.035
.597
.611
.177
.134
.153
.732
.197
.310
.343
.238
.782
-------
8-
7-
HEXflNE VflPOR PRESSURES
47.32 e 35 F ; 94.41 e 60 F ; 177.82 e 85
BOILING P01NT-69
TEMP-60
H
R
2-
1-
20 40 60 80 100 120 140
HOURS SINCE RPPUCRT10N
LEGEND: LOPDP.flTE - - 3
160 180 200 220
«-.« 10
Figure B.I.
Time relation of emission rate
and loading rate-Hexane,
295
-------
12H
11-
10-
9-
VRPOR PRESSURES
17 78 c 35 F : 35.48 t 60 F : 70.79 « 65
BOILING POINT=9i.65
TEMP=60
0-
60 60 100 120 140 160 160 200
HOURS SINCE fiPPLICRTlON
LEGEND: LOSDR3TE -^-- 3 > 6 «.-« 10
Figure B.2. Time relation of emission rate
and loading rate-3-Methylhexane,
temp. = 60°F.
220
296
-------
12-1
6-1
71
1
B-J
j
51
3-1
2-
'H
VRPOR PRESSURES
37.78 * ?5 F : 35.46 e 60 F : 70.79 e
BOILING P3INT-S3.B5
TEMP=B5
20 40
60
60 100 120 140 160
HOURS SINCE RPPL1CRTION
LEGEND: LOflDRflTE 3 6
Figure B.3. Time relation of emission rate
and loading rate-3-Methylhexane,
temp. = 85°F.
180 2GO 220
297
[^produced from
L^est avai'labU r»
-------
12-
11-
10-
E
M 9H
1
5
S
7-
R
A
; j
N
G 5-J
4-1
3-
2-
1-
0-
VflPOR PRESSURES
6.66 e 35 F ; 14.95 0 60 F : 31.62 e 85
BOILING POINT=109
LOflDRRTE=3
20 40 60 60 100 120 140 160 1BO 200 220
HOURS SINCE RPPL1CRTION
LEGEND: TEMP -~-* 35 « i « 6C *-.-- 85
Figure B.4. Time relation of emission rate
and ternperature-2,5-Dimethylhexane,
loading rate = 3.
298
-------
13-
12-
11-
10-J
E
M 9-|
1
5
5
1
0
N
7-
6-
3-
2-
1-
0-L
VRPOfi PRESSURES
6 66 e 35 F : 34.96 « 6G F : 31.62 e 65 F
B.5P BOILING P01N7-109
LORDRflTE-10
20 40 60 60 100 120 140
HOURS SINCE flPPLI.CfHlON
LEGEND: TEMP * 35 60
160 1BO 200 220
Figure B.5. Time relation of emission rate
and temperature-2,5-Dimethylhexane,
loading rate = 10.
299
-------
10-1
E
K
1
S
S
0
N
R
R
7
E
I
N
G
/
H
R
8-
6-
5~
3-
VRPOR PRESSURES
4.ii7 C 35 F ; 1C.5S e 60 F : 23.7] C 85
BOILING PClNT=iie.925
TEMF=6D
20
60
80 100 120 1UO 160
HOURS SINCE BPPLlCfiTION
LEGEND: LORORflTE -^ 3 6
Figure B.6. Time relation of emission rate
.. and loading rate-3-Methylheptane,
temp. = 60°F.
180 200 220
300
-------
10-1
8-1
E
M
I
s
s
1
0
N
fi
T
E
1
N
7-
6-
5-
VfiPOR PRESSURES
« 35 F ; 10.59 e 60 F : 23.71 e 65
BOILING POINT«118.925
TEMP-65
H
R
3-3
2-
1-
0-
20
>40
60
180 200 220
80 100 120 mo 160
HOURS SINCE RPPLlCflTION
LEGENO: LOflCRfiTE »--~- 3 * > B
Figure B.7. Time relation of emission rate
and loading rate-3-Methylheptane,
temp. = 85°F.
301
-------
10-j
9-
7-
E
M
I
S
S
3
0
N
R 5-
fi
2-
1-
0-
VflPOR PRESSURES
0 35 F : 10.55 e 60 F : 23.71 e 65 F
BOILING POINT-118.925
LOflDRflTE-3
20
40
60
60 100 120 l>iO 160 180 200 220
HOURS SINCE flPPLlCRTION
LEGEND: TEMP -~ 35 « 60 «.-«. 85
Figure B.8. Time relation of emission rate
and temper atur e- 3-Methy Iheptane ,
loading rate = 3.
302
-------
10H
9-
E
M
I
5
5
I
C
N
R
fl
T
E
1
N
7-
6-
VflPOR PRESSURES
4.147 C 35 7 : 10.59 « 63 F ; 23.73 e 85
BOILING POINT-11B.925
LORDRRTE-00
0-
20
LEGEND: TEMP
eo 100 120 mo
HOURS SINCE flPPLICRTlON
160
1BG 200 220
o.-.--. B5
Figure B.9. Time relation of emission rate
and temperature-3-MethyIheptane,
loading rate = 10.
303
-------
6-
E
M
I 5-j
s
5
I
0
N
3-
2-
0-
VflPOR PRESSURES
4.47 35 F -. 10 « 60 F s 19.95 e B5
BOILING POINT=124.084
TEMP»6C
20 40 60 80 100 12C 140 160
HOURS SINCE flPPUCRTlON
LEGEND: L502R3TE - 3 » 6
160 200 220
«-." 10
Figure B.10. Time relation of emission rate
and loading rate-2/2,5-Trimethylhexane,
temp. = 60°F.
304
-------
6-1
7-
6-
E
M
1 5-1
S
S
I
0
N
R 4-1
A
T
E
VRPOR PRESSURES
4.47 e 35 F : 10 e 60 F : 19.95
BOILING P01NT.124.0B4
LORORRTE-1D
85 F
3-
2-
1-
0-
20 40 60 BO 100 120 140 160 160 2CC 220
HOURS SINCE aPPLlCRTION
LEGEND: TEMP ~ 35 ' 50 »..--. 85
Figure B.ll. Time relation of emission rate
and temperature-2,2,5-Trimethylhexane
loading rate = 10.
305
-------
VflPOR PRESSURES
1.496 3S F ; 3.98 « 6C F ; 10 e 95 F
B01L1NC F01N1=}36.35)
LORDRRTE-3
0-
20 10 60 60 II 120 HO 160 1BO 200 220
HOURS SINCE RPPL1CRT10N
LEGEND: TEMP 35 -~-l « 60 «.-.-^ B5
Figure B.12. Time relation of emission rate
and temperature-l,4-Dimethylbenzene,
loading rate = 3.
306
-------
8-
7-
6-
5-
3-
2-
1-
VflPOR PRESSURES
1.496 0 35 F : 3.9B e 60 F : 10 e 85 F
BOILING P01NT=138.351
LORDRnTE=B
0-
20 40 60 60 100 120 140 160 180 200 220
HOURS SINCE flPPLICRTION
LEGEND: TEMP -~~ 35 » « 60 »-- 85
Figure B.13. Time relation of emission rate
and temperature-1,4-DimethyIbenzene,
loading rate = 6.
307
-------
9-1
8-
7-
VflPOR PRESSURES
1.496 35 F : 3.98 e 60 f -. 10
BOILING POINT-J36.351
LOflDRRTE-10
e 85 F
E
M
I
S
s
1
0
N
R
R
T
E
I
N
6-
5-
H
R
3-
2-
1-
o-
20 40 60 80 100 120 140 160 180 200
HOURS SINCE RPPLICRTION
LEGEND: TEMP *--- 35 60 *-.-* 85
Figure B.14. Time relation of emission rate and
temperature-1,4-Dimethylbenzene,
loading rate = 10.
220
308
-------
8-
7-
VflPOR PRESSURES
1.496 35 F : 3.98 60 F : 10 85
BOILING PCINT=138.351
TEMP=60
0-
20
40
60
80 100 120 mo 160
HOURS SINCE RPPLlCflTION
LEGEND: LORDRflTE - 3 6
ISO 200 220
«-« 10
Figure B.15,
Time relation of emission rate
and loading rate-l,4-Dimethylbenzene,
temp. = 60°F.
309
-------
6-
VRPOR PRESSURES
1.496 e 35 F : 3.98 * 60 F :
BC1L1NC P01NT-13B.351
TEMP-85
10 e 85
7-
E 6-
M
I
S
S
I
0 5-
N
R
fl
T
E 4-
I
N
G :
/ 3-
H
R
2-
1-
\
0-
20
140
60
160 200 220
BO 100 120 mO 160
HOURS SINCE RPPLlCflTlON
LEGEND: LOflDBRTE «-«.* 3 * 6
Figure B.16. Time relation of emission rate and
loading rate-1,4-Dimethylbenzene,
temp = 85°F.
310
-------
APPENDIX C
HEAVY METAL DATA
311
-------
TABLE C.I.
SOIL METAL DATA
(mg/kg)
Plot
1
2
2
2
§
3
3
^
4
4
4
4
5
5
5
5
6
6
6
7
7
7
7
7
7
7
7
I
8
8
8
Zn
8:8- :
30.o :
3618 i
63.0
.
56.0
30.0 2
32.0 2
3o.c ;
32.0 2
1 6 . C 2
14.0 i
37.0
48.0 1
29.5
27. C
46. C
45.0
41.0
40.0
38.0
36.0
43. C 2
40.0
45.0 I
43.0 I
38.0
36.0 t
40. C 2
26.0 2
62.0 2
66.5
66.5 1
63.5
67.0 1
67.0 2
87.0
79.5
46.0 ]
36.0
77.5 ;
37.0 1
33.0 2
Ni Cu
S.Q 12.0
52.0 22.0
E4.C 16.0
iO.O 12.0
22.0 12.0
16.0 140.0
4.0 110.0
8.0 15.0
!2.C 14.0
28.0 16.0
!2.0 14.0
>8.0 16.0
24. C 8.0
J6.0 10.0
4.0 38.5
1.5 98.5
0.0 37.0
1.0 25.0
1.5 66.0
0.5 74.0
9.C 43.0
7.5 31.5
3.5 31.5
7.0 16.0
>0.0 30.0
6.0 14.0
!0.0 55.0
!0.0 25.0
6.0 12.0
.0.0 14.0
4.0 14.0
(8.0 14.0
»8.0 170.0
5:8 U):8
9.5 170.0
8.0
M.O
6.0 10.0
5.0 9.5
6.C 30.0
4.0 32.0
'0.0 23.0
JO.O 24.0
Pb
JJ-jj
2o!o
20.0
20.0
24.0
20.0
18.0
20.0
20.0
20.0
20.0
40.0
40.0
12.0
5.5
16.0
16.0
1410
7.0
5.5
8.5
12.0
26.0
30.0
26.0
28.0
20.0
J8:8
20.0
40.0
12lo
22.0
22.0
14.0
14.5
20.0
20.0
23.0
25.0
Cr
11*8
104^0
98.0
66.0
32.0
22.0
92 0
80.0
92.0
80.0
108.0
76.0
23.0
26.5
21.5
11.0
30.5
24.5
30.5
35.5
21.5
24.0
27.0
92.0
31.0
23.0
80.0
112.0
86.0
74.0
102.0
24.5
24.5
24.0
26.0
20.0
22'. 5
70. C
60.0
26 . 0
22.0
Cd
8.00
.00
0.00
§.00
.00
.00
0.00
0.55
0.00
0.00
8:88
0.00
0.00
8:88
0.5C
0.00
8:88
0.00
0.00
0.00
0.00
0.00
Q-QQ
0.00
0.00
0.00
oloo
8:88
0.00
0.00
0.00
2.00
2.00
0.00
0.00
0.00
0.00
0.00
Date
( continued)
92282
100782
100782
100782
11178
1117!
111782
30282
70682
70682
92282
92282
00782
00782
00782
11782
11782
60983
60983
91082
91082
92682
111782
111732
312
Reproduced from
available
-------
Table C.I. (continued)
>lot Zn
9 12.0
9 36.0
9 52.0
9 35.0
9 48.0
9 31.0
9 47.5
9 28.0
9 33.0
10 41.5
10 40.0
10 36.5
10 38.0
10 84.0
10 29. C
10 45.0
11 39.0
11 34.0
12 30.0
12 24.0
13 36.0
13 47.5
3 50.0
3 51.0
: 1 ti: j
3 14.0
13 58.0
13 54.0
13 30.0
13 59.0
13 65.0
13 31.0
13 35.0
13 35.0
13 53.0
13 53.0
14 14.0
14 20.0
14 14.0
14 37.0
14 52.5
14 61.0
15 36.0
15 20.0
15 16.0
15 24.0
15 27.0
15 58.0
15 68.5
15 40.0
Ni
fj-jj
is!s
11.0
6.0
2.5
13.5
18.0
15.6
21.5
12.5
12-5
18.0
28. 0
11.5
16*0
1KO
28.0
28.0
24.0
12.0
11.5
12.5
U:8
16.0
32.0
30.0
90.0
11.0
10.5
16.0
12.0
21.0
17.0
13.0
34.0
32.0
0.0
12.5
14.5
13.5
16.0
36.0
32.0
10.5
islo
16.0
Cu
?§:§
111.0
11.5
11.1
11.5
75.0
20.0
21.0
11.5
9.0
9.0
10.0
8.0
20.5
25.0
54.0
24.0
8.0
8.0
14.0
10.0
9.5
10.0
11.0
4.0
8.0
180.0
50.0
10.0
130.0
149.5
24.0
18.0
24.0
11-8
13.0
8.0
4.0
4.0
92.0
112.0
154.0
8.5
6.0
8.0
19.0
24.0
141.5
193.0
34.0
Pb
20*0
slo
13.5
13.5
13.5
14.0
14.0
16.0
14.0
11.0
21.0
20.0
40.0
14.0
18.0
14.0
22.0
40.0
40.0
20.0
13.5
18.5
13.5
17.5
20.0
0.0
20.0
20.0
20.0
7.0
13.5
12.0
12.0
24.0
18.0
16.0
40.0
20.0
1.5
16.5
12.5
20.0
40.0
0.0
20.0
5.0
15.0
18.0
Cr
29l5
21.5
26.0
26.5
24.5
12.0
19.0
29.0
25.5
20.0
.
30.0
14.0
22.0
18.0
92.0
25.5
25.5
28.5
27.0
90.0
96.0
76.0
86.0
88.0
22.0
30.0
12.0
19.0
22.0
m
106.0
18.5
28.5
25.5
18.5
82.0
80.0
21.5
33.0
24.5
24.5
16.0
Cd
8:88
0.00
0.00
0.00
0.50
0.00
Q.OO
0.00
0.00
0.00
8.00
.00
0.00
0.00
8.00
.00
0.00
S. 00
.00
0.00
0.50
1.50
1.00
1.00
0.00
0.00
0.00
0.00
0.00
0.50
0.02
0.00
0.00
0.00
0.25
oloo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
8-QQ
.00
0.00
0.00
Dote
70682
70682
92282
92282
92282
92282
1C0782
111782
111782
60933
60983
60983
70682
70682
91082
110982
111782
111782
70682
70632
30282
60933
60983
60983
60983
70682
70682
92232
92282
92282
1C0782
1C0782
111782
111782
111782
122082
122082
706S2
70682
70682
92232
92282
1C0782
60983
70632
70632
91082
91082
92682
92632
110982
(continued)
313
-------
Table C.I,
(continued)
Plot
6
6
6
7
17
18
18
18
18
18
18
18
18
1 1
if
2D
20
20
20
20
20
20
20
2C
20
2C
20
20
2C
20
I?
21
21
21
21
22
22
22
23
il '
23
24
24
<4
24 1
it
Zn
\l:l
44lo
27.0
83.5
38.0
43.0
32.0
32.0
30.0
38.0
32.0
28.0
18.0
35.0
iS:8
32lo
46.5
45.5
48.0
45.0
43.5
34.0
26. C
14. C
36.5
39. C
44.5
47.5
39.0
38.0
45.0
33.0
66.0
61.5
79.5
30.0
.
33.0
72.0
90. C
24.0
42.0
45.0
64.0
39.0
&8
22. C
30.0
§1:8
53.0
47.0
Ni
2-Q
.0
5.0
' 6.0
' 2.C
' 8.5
14.0
16.0
26.0
24.0
28.0
48.0
22.0
32.0
28.0
35.0
36.0
32.0
0.0
25.5
19.0
10.5
11.5
12.0
34.0
26.0
26.0
?:8
11.5
11.5
13.0
14.0
17.0
16.0
' 0.5
1.0
3.0
: 4.0
' 4.0
' 1.0
' 2.5
13.0
24.0
23:8
20.5
18.0
fl'8
3s!o
20.0
17lo
19.0
Cu
182.5
H:8
2210
218.0
51.0
9.0
10.0
14.0
12.0
28.0
10.0
12.0
8.0
18.0
10.0
8.0
12.0
11.5
11.0
11.0
16.5
19.5
14.0
6.0
12.0
65.5
64.5
7C.5
57.0
71.0
66.0
96.0
'1:?
9.5
lolo
22.0
174.0
47.0
9.5
2s!o
57.0
120.0
80.0
?8:8
6.0
10.0
140IO
95.0
Pb
Cr
Cd
Date
13.5
1t:8
16.0
16.0
17.0
14.0
11.5
20.0
20.0
20.0
40.0
20.0
20.0
20.0
16.0
18:8
w
17.0
13.0
11.0
40.0
20.0
20.0
12.0
7.5
14.5
13.0
10.5
14.0
16.0
18.0
15.5
14.0
20.5
^ M *»
20.0
18.0
16.0
20.0
17.5
30.0
23.0
20.0
14.0
18.0
17.0
60.0
20.0
20.0
j!:8
29.0
26.0
21.0
i!i8
16^0
14.0
32.5
18.0
90.0
90.0
90.0
88.0
96.0
82.0
82.0
22.0
92.0
68lo
29.5
28.5
24.5
21.5
24.0
.
104.0
23.0
22.0
22.5
23.5
20.5
14.0
16.0
17.0
20.0
27.5
29.5
20*0
12lo
l?-2
27.5
98.0
26.0
29.0
27.5
16.0
16.0
.
.
?4lS
il:8
0.00
8l8o
oloo
0.00
0.00
0.00
8.00
.00
0.00
0.00
8:88
0.00
8:88
C.O
c.o
c.o
0.5
C.O
1.0
0.0
do
c.o
c.o
0.0
c.o
c.o
c.o
c.o
c.o
c.o
c.o
1.5
2.0
2.0
8:8
0.0
2.5
C.O
c.o
c.o
0.0
8:8
C.O
p. o
00
8:8
92682
111782
111782
111782
111782
92682
111782
60983
70632
70682
92282
92282
92282
92282
9228?
111782
70682
70682
30282
60983
60983
60983
60983
6098-3
70682
70682
70682
92282
92282
92282
92282
92382
111782
111782
111782
60983
60983
60983
91082
110982
111782
60983
60983
92282
111782
111782
92282
110982
110982
70682
70682
70682
110982
111782
111782
(continued)
314
Reproduced from
best available copy.
-------
Table C.I. (continued)
Plot'
4.
38.0
.0
45.5
12.0
I9-Q
39.0
?9-8
35.0
Ni
30.0
32.0
15.1
Cu
12.0
10.0
12.0
20.0
18.0
151.0
40.Q
75.0
10.0
10.0
8:8
22.0
fl:8
16.0
10.0
10.5
8.0
143.0
23.0
19.0
8.0
8.0
33.0
'Jo6:S
297.0
288.0
0.0
Pb
20.0
20.0
20.0
40.0
30.0
3.0
15.0
18.0
.0
.0
.
IS:
20.0
20.0
13.0
12.5
0.0
0.0
21.0
16.0
20.0
40. 0
7.0
18:8
il:l
22.0
17.0
13.5
20.0
15.0
Cr
24.5
185
I?:?
84.0
20.5
14.0
16.0
30.0
16.0
20.0
Cd
o
0.00
0.00
8:88
0.50
0.00
c.oo
0.00
0.00
0.00
0
1
0.00
0.00
8:88
o.oc
0.00
0.00
Date
30282
70682
70682
91082
91082
91082
mil
Sim
111782
111782
30282
60983
60983
60933
111782
111782
122082
'«2ii
70682
60983
60983
70632
92282
110982
11Q982
70682
70682
92682
HI
M
92682
111782
111782
Reproduced from
best available copy.
315
-------
TABLE C.2. BACKGROUND SOILS METALS
/ SAMPLE
i
i
1
2
5
4
5
6
7
8
V
10
U) 11
t- 12
o\ 13
14
15
16
17
18
19
, 1 20
0-50 21
in X ->
">TJ 22
TO 21
"g- 24
2.o ?S
n £ '
?Uo-
cr
CU
26.9
7.5
09.6
7.5
15.4
8.6
6.1
6.4
6.1
6.6
19.1
2D.8
24.0
12.1
6.5
6.3
3.0
6.1
5.6
5.2
5.9
1.1
6.6
3.2
_ 15.?
CR
47.6
11.8
5.8
14.3
19.1
15.6
6.8
7.6
?.5
11.3
16.9
29.2
8.7
12.4
12.3
10.4
14.3
11.4
9.7
8.2
8.6
8.1
9.8
11.3
22.1
PB
14.2
15.0
19.0
1?.0
27.0
12.9
8.9
4.9
13.9
12.9
20.8
12.0
18.0
14.0
18.0
18.0
16.0
14.0
6.9
17 .3
16.0
12.0
17.7
17.8
".4
ZN
35.2
77.5
26.1
35.9
29.1
19.8
19.1
19.0
42.8
42.4
36.2
34.6
30.3
24.1
34.1
21.2
19.0
24.6
21.6
31.0
89.1
41.2
54.2
NI
65.1
21.3
16.7
25.3
21.4
33.0
20.6
15.9
15.6
14.4
27.2
43.1
15.3
31.0
22.1
21.7
3.9
31.5
9.5
13.2
16.9
30.1
14.3
13.6
30.8
CO
0.8
0.5
0.2
0.9
1.4
0.6
1:!
0.5
0.0
0.2
0.1
2.5
0.0
0.0
0.0
0.2
0.0
0.0
0.0
0.0
0.3
0.0
0.0
0.0
n|
rt I
-------
TABLE C.3. SLUDGE ANALYSIS BY BATCH
Batch
1
2
3
3
3
3
3
3
3
4
4
4
4
4
4
Zn
12.97
25.49
812.20
293.34
500.39
392.92
344.29
216.17
70.65
101.94
177.34
145.89
258.99
319.64
258.82
Ni
22.20
12.57
22.62
12.54
12.71
10.28
5.71
11.16
8.09
8.39
7.72
6.36
5.06
21.04
14.82
mg/kg)
Cu
1.00
0.47
19.37
8.46
9.71
7.01
2.86
5.41
1.80
5.81
8.57
7.73
6.74
1.80
9.26
Pb
2.00
1.12
50.26
20.84
22.46
19.62
37.14
11.50
5.10
4.84
11.29
12.27
18.54
5.10
12.96
Cr
0.00
1.65
-
20.21
25.42
24.29
27.14
23.05
16.67
7.74
14.29
12.27
12.92
23.05
10.65
Cd
0.25
0.00
-
13.48
23.30
16.35
14.29
20.04
10.65
1.29
7.43
8.18
8.99
20.04
16.67
317
-------
TABLE B.4. EMISSION RATES OF MEASURED HYDROCARBONS
Temp = 85, Loading Rate = 3%
to
oo
u>
TINE SINCE flPPL. IHOUnSI
COMPOUND NRME
. PENTHNE
. CTCLOPENTRNE
. HEXRNE
, HETHTL CTCLOPENTRNE
. BEN/ENE
. 2.4-DINETHTLPENIRNE
CTCLOHEXHNE
. 3-NETHTLHEXHNE
MEIHTLCKLLOHLXRNE
i 2.5-OIMETHTLHEXRNE
I. 2.3.4-IRIMETHUPtNTRNE
2. 3-METHHMEP1HNE
3. 2.2.5-THIMElMTI.Hf XONE
4. 1.4-DIME1HTLBEN/ENE
SUM OF IM COMPOUNDS
TOIRL VOIHT. RS HFXRNE
X |i| COMP/T01RL VOIMI
.033
0.416
0.916
6.878
3.594
2.6
16.7
4.272
8.839
7.252
7.871
33.018
7.218
M . R8 7
5.326
I09.5H7
1/7. 779
22.94
. 166
0.397
0.935
4.508
2.26
2.212
12.81 1
2.828
7.9B3
4. 746
6. SI 1
26. 096
3.9/2
4.?7'J
5.203
85. 3? i
:)4i.27u
25.01)
1.0
0.29
0.959
I.l!i4
3. in
3. SIS
4.544
1.272
2.311
4. 759
2.98M
10.255
2.3MS
3.259
3.GM?
MM.SH9
136.508
32.66
3
:RRMS /
U.OIB
O.M7
f).3!3
0.27
o.nm
1.707
0.262
0.76M
I.MCS
0.9(i/
3.527
0.856
I.2IC4
1 .51) IS
I3.7r,3
59.72?
23.05
2M
HOUR / 1
0.003
0. 107
0.20M
0.036
0.07M
0. 153
0.023
0.2M8
0.398
0.682
I.3B2
O.M26
0. 7m
I.37M
5.H2M
25.595
-------
TABLE B.5.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
to
03
Temp. = 85, Loading Rate =6%
HUE SINCE RPPL. (HOURS)
COMPOUND NRME
1. PEN1HNE
2. CtClOPENIRNE
3. HEXRNE
4. NE1HTL CTCLOPENTRNE
5. BEN/ENt
6.2.4-OIMETHTLPENTRNE
7 CtCLOHEXHNE
*. 3-HETHII HEXHNE
9.ME1HTLCTCI OHEXHNE
10. 2.5-OIHEtHHHEXHNE
II. 2.3.1-THIME1HTIPENTRNE
11. 3-HETHTI.HhPIHNE
13. 2.2.5- IHIMnilTl HEXRNE
U. 1.4-OIMHHTLBEN/ENE
SUM at 14 COMPOUNDS
TOTRL VCIlHT. RS HFXRNE
1. IM COHP/I01RL VIU HI
.033
0.38?
0.402
8.848
4.42
2.694
20. 156
5.388
10.002
8.254
9.988
34.008
6. 104
4.49
4.08
1??. 176
548.000
22.29
.166
0.342
0.46
7.419
3.6G
2.45
20.085
4.708
9.711
I,. 7 73
9.345
33.365
8 . 6 76
4.304
U. MB
II r, . o I ti
394.480
29.41
.50
I
0.336
0. II
2. 19
3.304
2. 168
11.906
2.098
3.685
6.147
4.?07
I6.0U9
4.ti09
2.318
4.5-..S
C.S.f '!,"
235. H89
26. 9H
1
1HHMS / 1
0.0107
0.078
1 . (106
0.52')
0.453
4.97
0. 793
2.496
1 .249
3. 115
1 1.8)6
4.2H7
i'.?'!/
M.IIIV
3 1 . .? 1 ,n
U5.50H
27.46
5
HOUR / 1
6.04
0.314
0. 168
U.204
1.86
0.21
1.074
0.514
1.448
3.554
1.65
1. 19
i>.6?4
I4.B50
04.284
M. 10
24
80 SO. FT
0.058
0. 1836
0. 135
0. 161
0. 197
0.086
0.3939
0.128
0.264
1.438
0.376
0.3R7
1 . 34 1
5. I4H
2H. 154
III. 29
48
. IPLOI
6.021
0.018
0.1021
0.09
0. 104
0.051
0.479
0.0)4
0. 198
0.324
0.169
0..--3
0.552
2.412
25.598
9. "12
48.5"
RREHI
0.022
1.34
0.08
0.598
0.742
0. 194
0.098
0.268
0.61)0
0.066
1. 1 14
0.594
O.H5
2.516
I.RflO
63. 135
IS. 1.5
168
0.0405
0.945
0.017
0.26
0.372
0.038
0.068
0.042
0.0375
0.091
0. 15
0.331
0.245
0.433
3.070
2l.9:iH
13.99
168. 5«
0.095
0.946
0. 1 13
0.382
0.52
0.052
0. 193
0.083
0.047
0.0-J5
0.4'i
1.082
0.646
1.928
6.612
46.415
14.^!)
192
0.006
0. 172
0.02
0.048
0.084
0.046
0.02
0.04
0.028
0.81
0. 18
0.324
0.466
0.502
2.H,T,
30. l\0
9.20
SOIL RNO SLUDGE MIXTURE MRS 1ILLFO
-------
TABLE B.6.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
N)
CO
(J1
TIME SINCE HPPL. (HOURS)
Temp
.166
COMPOUND NAME
1.
2.
3.
4.
).
6.
7.
a.
9.
10.
11.
12.
13.
14.
PEN1HNE
CTCLOPENIflNE
HEXflNE
METHTL CTCLOPENIflNE
BEN/tNf
2.4-OIHETHTI.PENTHNE
CtCLOHLKflNE
3-METHTlHEXflNE
MEIHTLCTCLOHrXflNE
2.5-OIMElHYLHEXflNE
2.3.4-iniMElHHPENTflNE
3-MEIHTLHEPIBNE
2.2.5-1MIME IH1I HEXRNE
1.4-DIMtlHnQlNZfNE
SUM OF 11 COMPOUNDS
TOIflL VOII1I. IIS HI XflNE
7. 14 COMP/lOlfUVOl
0.3914
0.404
8. 198
3.68
2. 75
21.58
3. 136
1 1.658
9.33
13.284
4t. V26
9.61?
7. 77
8.536
147.288
400. 7i5
31 .97
= 85,
1.0
Loac
8.0
ii
ng ]
24
CRRMS / HOHR / 180
0. 166
1.069
?.65S
2.355
1.87
9.HI7
2.8U5
5.229
3. IliM
5.6H9
22. 71
5. 496
3.(i9M
5.H5M
72.053
3G7. IMS
23. If
0.006
0.639
n.88
0.756
U.BI2
3. 104
0. l?3
1.98
1.426
2. 126
7. 144
3.028
2.05
4. 50?
2H.G16
1 HI . 9 1 3
?S.8?
0.
0.
0.
0.
1.
0.
0.
0.
1.
0.
2.
0.
0.
1.
10
42
25
03
577
07
844
212
736
192
404
034
774
146
902
02
092
.1133
.658
.40
Rate :
96
= 10%
96.5*
192
216
SQ.FT. IPLOI flREfl)
0.026
0.423
0.079
0.44
0.711
0. 196
0.096
0. 139
0.521
0.22
0.591
0.492
0.521
0.8P7
5.2H2
28.030
18.84
0.036
1.293
0.084
0.816
1.236
0.3
0. 109
0. 182
O.G14
0.964
1.286
0.919
1.306
2. 187
11.332
59.722
lfl.97
0.022
0.22
0.064
0.074
0. 144
0.084
0.032
0.3
0.074
0.816
0.504
1.426
1 . 024
1 .56
6.344
24. Ilil
2G.2C,
0.
6.
6.
0.
0.
0.
0.
0.
0.
0.
0.
1.
3.
14
2r>
032
028
01
054
008
212
008
224
274
758
532
19
3jn
.G,'5
. 7?
SOU flNO SlUOr.E MIXMIRE WHS I II I ED
-------
TABLE B.7.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
to
00
Temp = 60, Loading Rate =3%
1IHE SINCE HPPl. IHOURSI
COMPOUND NflME
1. PENIHNE
2. CTCIOPENTHNE
j HEXRNE
4. HE1HTL CTCLOPENTRNE
. BENZENE
t'. 2.4-OIME1HHPEN1RNE
7.CTCL8HEXHNE
$ 3-METHUHEXHNE
9.NE1HUCTCLOHEXRNE
10. 2.5-OIMEtHTLHEXRNE
11.?. 3.1- in IMF Timer NIHNE
12. 3-ME1H1LMEP1RNE
13 2.2.5-1RIME1HUHI XRNE
14. I.M-OIMFIHILBENHNI
iniHI VOlfll. RS Ml XRNE
REROINf, FHOM SNIFI f.R
'/. 114 COMP/101HI. VOLH1
.033
0.026
0.082
3.766
2.7B2
1.2MB
2.M76
I.08B
7.68
b.003
3.202
9. -992
1.536
3.506
3.6B
Ml,. 156
107. IMM
15.01
1.0
0.088
0.356
0.657
1.62M
l.ll
2.002
1.228
2.516
4.098
2.6M2
9. MOM
l.,>f]8
1.018
2.IB7
31. IOH
1S.I.5M
20. ?6
3.0
0.0082
n. in?
O.M3G
0.3IM
0.3HH
1.70?
0.332
(I.8U2
U.hllO
0.9M
3.8'i2
O.HS6
0. V',B
O.flill)
1 1 . Ill'l
OI.M^B
19.51
2M
GRRHS /
n.nns
0. 10M
o.oor
0.3
0.3^8
0.069
0.06
0.092
O.M .
0. 152
(1.612
0. 162
6.MGr.2
3. Ibli
10. 7G9
1 7 . OH
M8
HOUR / 1
0.003
0.06
0.006
0.0MB
0.071
0.057
0.015
0.057
O.OGIi
0.102
0.21
0. 128
0.105
0.3119
I.2MO
5.210
?1.HO
48. 5"
180 SO. F
0.039
0.032
0.28
0.2M6
0.378
0.06B
0.26B
0.312
0.252
0.592
1. 108
0.756
0. 708
1.52
6.559
V.M20
?0.?3
72
t. IPLOT
0.0051
0.057
0.019
0.172
0.102
0.0MB
0.022
0. 156
0. IM8
0.262
0.507
O.M1M
0.315
1.293
3.SPO
15.357
-------
TABLE B.8.
to
CO
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp = 60, Loading Rate = 6%
TIME SINCE flPPL. IHOURSI
COMPOUND NRHE
I.
2.
3.
4.
3.
6.
7.
a.
9.
10.
11.
12.
13.
14.
PENTRNE
CTCLOPENIRNE
HEXRNE
HETHTL CTCIOPENTHNE
BENZENE
2.4-OINE1HTLPEN1RNE
CTCLOHEXRNE
3-METHTLHEXRNE
HETHTLCTCLOHEXRNE
2.S-OIME1HYLHEXRNE
2.3.4-1RIHFTHILPEN1RNE
3-HETHTLHEP1RNE
2. 2.5-1HIMEMUI HEXRNE
1.4-DIMEtHTl.HFNZtNF
SUN OF IM COMPOUNDS
TOTHL VOLflt. RS HtXONE
X IM COMP/101HL VOLRT
.033
0.313
0.30M
5. 872
4.722
2. 84?
13. 132
1.692
7.196
6.791
5.69G
26. 65
3.098
1.314
3.738
06.562
341.270
25.36
6.0
0.024
0.294
0.428
0.36
0.32
2.02
0.3M2
0.965
0.561
0.599
3.33
0. 788
1.318
1.372
12. 724
37.510
33.92
24 48 48.5. 72 96 96.5-
CRHMS / HOUR / 180 SO. FT. (PLOT flRERl
0.0041
0. 109
0.037
0. 171
0.297
0.349
0. 137
0.359
0.405
0.292
0.729
0.48
0.539
3.9fifl
20.476
19.48
0.00?
0.085
0.018
0.085
0. 194
0.236
0.026
0. 104
0. 139
0.213
0.632
0.333
0.226
0.42>
2.725
20.376
13. 37
0.022
0.24
0.298
0. 122
0.294
0.596
0.23S
0.309
0.253
0.601
1.897
0.73
0.761
1.168
7.526
54.603
13.78
0.016
0.125
0.078
0.094
0. 109
0.22
0.086
0.169
0. 131
0.225
0.628
0.4J6
0.456
0.544
3.317
20.476
16.20
0.004
0. 189
0.023
0.077
0.104
0.074
0.014
0.072
0.099
0. 112
0. 186
0. 12
0.246
0.29
1.612
1 1.944
13.50
0.01
0.266
0.05
0.086
0.204
0. 184
0.024
0.117
0. 136
0.251
0.521
0.41
0.428
0.655
3.362
32.420
10.37
120
0.006
0.162
0.065
0.054
0.072
0.076
0.014
0. 104
0.088
0.12
0.086
0.208
0. II
0.36
I.S45
13.650
1 1.32
146
6.004
t
0.001
0.003
0.091
0.004
0.052
0.043
0. 125
0. 125
0.239
.
0.33
1.017
8.S31
1 1 . 'J2
SOU RNO SLUDGE HIXlURC MRS 1II.IEO
-------
TABLE B.9.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp =
TIHE SINCE HPPL. IHOURSI
1^ COMPOUND NHME
DO
00 1. PENTHNE
2. CTCLOPENIHNE
3. HEXRNE
4. MEIHTL CTCLOPENTRNE
3. BENZENE
6. 2.4-OIHETHTLPENIRNE
7. CTCLOHEXRNE
8. 3-HEIHtLHEXRNE
9. METHTLCTI LOHEXHNE
10. 2.5-OIHEIHTLHEXRNE
II. 2.3.4-TRIME1HTLPEN1RNE
12. 3-METHTLHEP1HNE
11. 2.2.5-TRIMEIHTLHEXHNE
V Vw
£.T>
"a.
if
??:
oi
TJ
X
14. I.4-DIME1HTLBENZENE
SUM Or 14 COMPOUNDS
TOIRL VOLRI. RS HEXRNE
'/. 14 COMP/IOIflL VOLRI
.033
0.252
0.296
6.09
6.648
1.042
15.47
4.014
7.388
6.955
6.204
28.99
5. 164
4.606
4.667
97.786
307. 143
31 .84
.50
0. 126
0. 189
3.384
1.518
1.445
9.8BG
2.0J6
4.945
2.67
4.727
19.45
4.581
2.335
4. Ill
61.150
304.016
20.21
1.0
0.098
0.308
2.281
1. 144
0.971
4.938
1.644
2.925
2. 101
2.037
7.644
2.914
1.304
2.86
3_<. 167
203.000
Id. J4
= 60,
4
GRRMS /
0.01
0.286
2.431
0.37
0.41
3.055
0.5J5
1.536
0.0:19
1. 773
7.227
2.0J9
1.272
2.2B3
24.046
1 70.635
14.09
Loading Rate = 10%
24
HOUR /
0.006
0.251
0. 12
0. 161
U. J24
0.6
0.393
0.628
0.07
0.186
1.375
0.508
0. 704
O.HH3
fi. HUH
27.813
24.84
48
180 SO. FT
0.002
0.205
0 . 04 1
0.096
0. 196
0.271
0.035
0.143
0. 142
0. 194
0.69
0.227
0.369
O.S48
3. 159
2G.448
1 1.94
48.5-
. (PLOT
0.029
0.316
1.28
0.32
0.25
2.202
0.248
0.867
0.2U
1.345
4.7
1.557
0.98
1.565
15.919
88. 730
17.94
54
RRERI
0.006
0. 139
0.098
0.242
0.05
0.328
0. 142
0. 194
0.092
0.702
1.094
0. 74 1
0. 78
0.834
5 . 442
30.774
I7.lifl
72
0.017
0. II
0.072
0.095
0.113
0.281
0.141
O.OG6
0.262
0.613
0.364
0.318
0.517
2.999
23.868
12.56
96
0.007
0.325
0.064
0.016
0.041
0.208
0.033
0. 102
0.049
0.209
0.603
0.304
0.251
0.99
3.202
11.841
27.04
96. 5«
0.02
0.362
0.264
0. 172
0.242
0.587
0.05
0.36
0.201
0.699
1.933
0.942
0.025
1.215
7. 7<,2
44. nun
I7.li2
1MB
0. (!<".
0 . 2 / /
0.012
0.2117
0.224
0.09H
o . 0:1 7
o. i r,
oi'lHH
0..14IJ
0.3H8
0.4 H,
0 . li 1 I.
1 . 2 1 ti
ii.i.Mi
2.1. M,
. SOIL RNI) SLUDGE MIXTURE HRS llllfO
-------
TABLE B.10.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
Temp = 35, Loading Rate = 3%
to
oo
TIME SINCE RPPL. (HOURS!
COMPOUND NflME
2.0
6.0
48. 5*
GRflMS / HOUR / 180 SQ.FT. IPLOT RREHI
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
PENTRNE
CYCLOPENTRNE
HEXRNE
METHYL CYCLOPENTRNE
BENZENE
2.4-DIMETHYLPENTRNE
CYCLOHEXRNE
3-METHYLHEXRNE
METHYLCYCLOHEXRNE
2.5-DIMETHYLHEXRNE
2.3.4-TRlMt:THYLPLN!flNE
3-METHYLHEPIflNE
2.2.5-TRIMETH1LHLXMNE
1.4-DIMETHYLBENZENfc
SUM OF 14 COMPOUNDS
TOTRL VOLRT. RS HUXHNC
'/. 14 COMP/TOTRL VOLHT
0.
0.
0.
.
0.
.
.
0.
0.
0.
3.
0.
2.
1 .
1 1
1 1
9.
11 1
122
386
478
617
GOO
792
303
786
398
287
.048
9.000
28
0.
0.
0.
0.
0.
.
.
0.
0.
0.
0.
0.
1.
0.
4.
32
13
035
198
183
198
172
164
252
191
69
266
609
573
5 3 1
. 761
.03
0.
0.
0.
0.
0.
.
0.
0.
0.
0.
0.
0.
0.
0.
1 .
5.
19
034
068
U09
034
083
029
056
1 14
094
21G
13
1
192
159
972
.41
0.
0.
0.
0.
0.
0.
.
0.
u.
0.
0.
0.
0.
0.
2.
22
10
0
1
0
1
1
1
1
1
1
2
2
2
3
2
B
73
Ih
1 1
47
32
73
52
67
OR
59
G
14
B
70
182
23
SOIL RND SLUDGE MIXTURE WRS TILLED
-------
TABLE B.ll.
EMISSION RATES OF MEASURED HYDROCARBONS
BY GAS CHROMATOGRAPHY
to
VO
o
Temp = 35, Loading Rate = 6%
TIME SINCE RPPL. (HOURS)
COMPOUND NflMII
.50
9G
146
GF1RM5 / HOUR / 180 SQ.FT. (PLOT flREfll
1. PENTRNE
2. CYCLOPENTRNE
3. HEXRNE
A. METHYL CYCLOPENTONE
5. BENZENE
6. 2,4-DlMETHYLPENIRNE
7. CYCLOHEXflNE
8. 3-METHYLHEXRNE
9. METHYLCYCLOHLXRNE
10. 2.5-DIMETHYLHEXRNE
11. 2.3.4-THIMEFHTl.Pt.NrnNE
12. 3-METHYLHtPTRNE
13. 2.2.5-TRIMCTinLHEXRNE
14. l.M-DIMETHYLDCNZENE
SUM OF 1H rOMPillINO'^
TOTRL VOL.R1. RS HFXRNE
'/. 14 COMP/TOTflL VOt rtl
0.?3G
O.IIG3
1.M99
i .nse
1.S92
^.302
1.347
3.G23
3.53
2. 1
fl.lH48
2.903
2. 24 3
2.022
3G.rir,G
187. G98
1 9.148
0.085
0.16V
0.091
0. 125
0.21 B
0.20G
0.04
0.113
0.21R
0 . 1 G,7
0.501
0.229
0. K:iG
0.3V.b
2.G79
10. 2 38
2G. 1 7
0.039
0. 163
0.007
0. 1G
0.164
0.047
0.04H
0.033
0.217
OJJ9
0.094
0.08
U . 0 7 1
0. 149
1 . 762
5.119
34.42
* SOIL DNP SLUDGE MIXTURE WRS TILLFD
------- |