EPA R2-72-110
DECEMBER 1972
Environmental Protection Technology Series
Oily Waste Disposal by
Soil Cultivation Process
.588.
Ol
O
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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December 1972
OILY WASTE DISPOSAL
BY SOIL CULTIVATION PROCESS
By
C. Buford Kincannon
Project 12050 EZG
Project Director
Leon H. Myers
Robert S. Kerr Water Research Center
P. 0. Box 1198
Ada, Oklahoma 7^820
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Onice
Washington, D.C., 20402 - Price $'J
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents neces-
sarily reflect the views and policies of the
Environmental Protection Agency, nor does mention
of trade names or commercial products constitute
endorsement or recommendation for use.
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ABSTRACT
Disposal of oily sludges by utilizing soil microorganisms to decompose
the oil has been demonstrated at prevailing soil and climatic conditions
at Deer Park, Texas. The oil decomposition rate was about 0.5 lbs/ft3
of soil per month without fertilizers and about 1.0 lb/ft3/month when
fertilized. The rate of 1.0 Ib/ft3/month is about 70 bbls/acre/month
using the upper 0.5 foot of soil. Costs of the soil disposal method,
including fertilizers, were about $7.00/bbl of oil and $3.00/bbl of
sludge containing 33 percent oil. Major microbiological species active
in the soil were members of the genus Arthrobacter, Corynebacterium,
Flavobacterium, Nocardia, and Pseudomonas.
Differences in decomposition rate and microbial species due to hydro-
carbon type as present in crude, bunker C, and waxy raffinate oils
were minimal.
Infrared and gas chromatography examinations of oil extracted from
fertilized and unfertilized soils showed differences in organic acid
contents and boiling ranges.
Oil and fertilizer chemicals did not infiltrate vertically into the
soil at the test location under prevailing conditions.
Rainfall runoff water contained 1) up to 100 ppm extractable oils found
to be naphthenic acids and 2) up to 150 mg/1 ammonia as N when the
nutrients were excessive in the soil.
This report was submitted in fulfillment of Project Number 12050 EZG,
under the (partial) sponsorship of the Office of Research and Monitor-
ing, Environmental Protection Agency.
iii
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CONTENTS
Section Page
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Oily Sludge 7
V Project Description and Objectives 9
VI Soil Test Plots 11
VII Soil Nutrients (Fertilizer) 15
VIII Startup, Operation, and Appearance 17
IX Sampling and Testing 23
X Effectiveness of the Cultivation Process 27
Oil Decomposition Rate and Effect of Fertilizer 27
Metals Contents of Soil 39
Oil and Nutrient Infiltration 39
XI Quantity and Cost Based Upon Conditions During
the Project 41
XII Microbial Action 43
XIII Composition of Oil Extracted From the Soil 47
Hydrocarbon Types 47
Infrared Spectres copy 47
Gas Chromatography 53
XIV Rainfall Runoff 59
XV Acknowledgments 61
XVI References 63
XVII Appendices 65
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FIGURES
Page
1 EXPERIMENTAL PLOTS 10
2 PREPARATION OF TEST PLOTS 12
3 SOIL PLOT IDENTIFICATION MARKERS 13
4 SOIL CULTIVATION AND ADDITION OF OIL 18
5 BEFORE AND AFTER SECOND ADDITION OF OIL TO "A" PLOTS 19
6 BEFORE AND AFTER SECOND ADDITION OF OIL TO "B" PLOTS 20
7 BEFORE AND AFTER SECOND ADDITION OF OIL TO "C" PLOTS 21
8 SOIL AT END OF THE DEMONSTRATION PERIOD 22
9 TYPICAL SAMPLING POINTS 25
10 OIL CONTENT OF SOIL, "A" PLOTS 28
11 OIL CONTENT OF SOIL, "B" PLOTS 29
12 OIL CONTENT OF SOIL, "C" PLOTS 30
13 NITROGEN CONTENT OF SOIL, PLOT A-l 31
14 NITROGEN CONTENT OF SOIL, PLOT A-2 32
15 PHOSPHORUS CONTENT OF SOIL, "A" PLOTS 33
16 TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP, "A" PLOTS 35
17 TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP, "B" PLOTS 36
18 TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP, "C" PLOTS 37
19 MICROBIAL CONTENT OF SOIL FROM "A" PLOTS 42
20 MICROBIAL CONTENT OF SOIL FROM "B" PLOTS 44
21 MICROBIAL CONTENT OF SOIL FROM "C" PLOTS 45
22 HYDROCARBON TYPE OF OIL EXTRACTED FROM "A" PLOTS 46
23 HYDROCARBON TYPE OF OIL EXTRACTED FROM "B" PLOTS 48
vi
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FIGURES (CONTD.)
Page
24 HYDROCARBON TYPE OF OIL EXTRACTED FROM "C" PLOTS 49
25 INFRARED SPECTRA OF OILS EXTRACTED FROM "A" PLOTS 50
26 INFRARED SPECTRA OF OILS EXTRACTED FROM "B" PLOTS 51
27 INFRARED SPECTRA OF OILS EXTRACTED FROM "C" PLOTS 52
28 GAS CHROMATOGRAPH AND BOILING POINT PROFILES,
"A" PLOTS 54
29 GAS CHROMATOGRAPH AND BOILING POINT PROFILES,
"B" PLOTS 55
30 GAS CHROMATOGRAPH AND BOILING POINT PROFILES,
"C" PLOTS 56
VI1
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TABLES
No. Page
1 Nutrients Added During the Study 16
2 Sampling and Testing Frequency 24
3 Oil Decomposition Rate 38
4 Quantity and Cost Based Upon Experimental Conditions 40
viii
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SECTION I
CONCLUSIONS
1. Disposal of oily sludges (hydrocarbon) by microbial action in culti-
vated soil has been demonstrated at prevailing soil and climatic
conditions at Deer Park, Texas.
2. Three simultaneous experiments with three oils, i.e., crude oil,
bunker C fuel oil, and waxy raffinate oil, indicated decomposition
rates for the three oils to be approximately equal and averaged
about 0.5 pounds of oil per cubic foot per month without adding
nitrogen and phosphorus nutrients and about 1.0 pound per cubic
foot per month when fertilizers were added. This is equivalent
to about 70 barrels of oil per acre per month.
3. Cost of the soil cultivation process based on the demonstration
project expenses and a disposal rate of 70 barrels of oil per acre
was $7.00 per barrel of oil. Assuming oily sludges and waste
materials contain 33 percent oil, the disposal cost by the soil
cultivation process would be about $3.00 per barrel.
4. An optimum fertilization program appears to be a) the initial addi-
tion of chemicals, if needed based upon soil test results, to
attain a slight excess of nitrogen, potassium, and phosphorus, and
b) test at regular intervals, once per month, for ammonia and
nitrate contents of the soil and add small dosages of ammonium
nitrate as needed to maintain a positive test result (10-50 ppm)
for ammonium and/or nitrate contents.
5. The major species of microorganisms present are members of the
genus Pseudomonas, Flavobacterium, Nocardia, Corynebacterium, and
Arthrobacter. The nature of the hydrocarbon substrate did not
appear to influence the type of organisms present but did affect
the number of bacteria in the soil. Crude oil tank bottoms pro-
duced the highest count, waxy raffinate oil produced an inter-
mediate count, while bunker C fuel oil exhibited the lowest
microbial population. Temperature appeared to have no effect upon
the microbial count and distribution. Addition of fertilizer did
not affect the microorganism distribution but appeared to be
directly related with the total aerobic count.
6. Oil decomposition rates were low when the concentration of oil in
the soil approached the starting condition of 10 percent oil in
the soil. Also, the low reaction period coincided with the winter
months and low temperature period.
7. Both aromatic and saturated hydrocarbons were reduced with time in
the soil for crude oil tank bottoms and bunker C fuel oil. Only
the saturate fraction of waxy raffinate oil appeared to be reduced
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by soil microbial action at conditions existing during the project
period.
8. Infrared and gas chromatographic analyses of the oil added to and
extracted from soil indicated a) the absence of organic acids in
oils added to the soil and the presence of organic acids in each
of the extracted oils (oils from plots that were fertilized showed
higher concentrations of organic acids), b) the organic acid in-
crease coincided with a decrease in total saturates, and c) the
percent weight boiling less than 500°C generally was lower for the
oil extracted from the soil at the finish of the project than for
either the oil added to or the oil extracted from the soil at the
start of'the project (the lowest percent weight boiling up to 500 C
was extracted from soil which had received the largest quantity of
fertilizer materials).
9. Oil and fertilizer chemicals did not infiltrate vertically into the
soil at the test location and condition.
10. Rainfall runoff water contained 30 to 100 ppm oil. This oil
appeared to be essentially naphthenic acids based upon infrared
inspection of oil fractions. Also, rainfall runoff water contained
ammonia (nitrogen nutrient) approximately proportional to the
excess ammonia content of the soil. Phosphorus and-nitrates were
not found in runoff water.
11. Oil and nutrient contents of rainfall runoff water from the soil
cultivation process can be relatively high, and this discharge
water should receive treatment before entering public waterways.
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SECTION II
RECOMMENDATIONS
This project demonstrated that soil microorganisms decompose petroleum
oily waste and that oil and fertilizer chemicals did not penetrate the
soil at the location and conditions of the test. However, numerous
factors are left unresolved and future experiments should gain
knowledge concerning the following uncertainties:
1. The residual oil in the soil after the 18-month project contained
organic acids, and those soluble in rainfall runoff water were
primarily naphthenic acids. Since most organic acids are water
soluble, this suggests that naphthenic acids do not decompose in
the soil as rapidly as aliphatic acids or that naphthenic acids
are formed from aliphatic or aromatic materials at the soil condi-
tions. Speculatively, large concentrations of naphthenic acids
may inhibit microbial growth in the soil, and water washing of
these organic acids from the soil to a separate biotreatment
system might improve the oil decomposition rate in the soil.
2. Residual oil extracted from the soil was characterized by infrared
to be polyaromatic oils, suggesting this hydrocarbon group to be
slow reaction or nonreactive for microbial decomposition at the
prevailing conditions. Certain, and yet unknown, environmental
conditions might improve the decomposition rate of the poly-
aromatics.
3. Accumulation and buildup of metals or salts contents with long-
range usage perhaps affects the microorganism activity. The
acidity or alkalinity range, optimum for microbial action, may
vary with the soil contents.
For application of the process, the following items must be considered:
1. The time required for native soil bacteria to become acclimated
oil decomposers likely depends upon the soil composition and
temperature.
2. Since soil profiles vary, tjhe oil penetration rate into soil needs
to be determined at the location where the process is to be used.
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SECTION III
INTRODUCTION
Petroleum crude oil, fuels, and lubricants become waste components
when emulsified with water, solids, and/or debris and are potential
contaminants of surface and subsurface waters. The volume of oily
waste is potentially large due to large quantities of petroleum oils
handled and used. Sources of the waste are from spillage of crude
oil and refined products and from petroleum refinery operations.
This paper deals with the refinery operation, but the findings are
expected to be applicable for most petroleum sludges.
When large quantities of oil are accidentally spilled on seawater,
inland water, or land, much of the oil can often be recovered, but some
emulsified waste oils are formed. Removal and disposal of these oily
wastes are separate problems for each accident. Also, refining of
petroleum crude oil into fuels, solvents, waxes, and asphalts results
in small quantities of oily waste materials. These oily sludges
obtained on an infrequent basis may be accumulated in a temporary
storage vessel or disposed of on a more or less continuous basis.
Waste oils from refinery processes and from oil spills are similar
in composition.
One method for disposal of oily sludges has been by mixing with the
soil and utilizing soil microorganisms to decompose the oil. Applica-
tion of this method (referred to also as land spreading operation) at
several refineries has been reported, and a modification of the method
was used during the Santa Barbara oil spill.2 Wet oil-straw-sand
mixture removed from the beaches was disposed of as solid waste in a
land fill, and presumably the straw and oil decomposed by microbial
action. Many investigations have shown that some microorganisms
normally present in the soil will attack petroleum hydrocarbons and
utilize them as their sole source of carbon. The reaction is
dependent upon many interrelated conditions, which have not yet been
fully understood, such as temperature, moisture, soil properties
(physical and chemical, including nutrient content), oil content and
properties, microbial content, acclimation period, and the availability
of oxygen and nutrients. Poorly aerated soils become anaerobic and
under these conditions the microorganisms decompose organic matter
very slowly. Aeration of the soil by frequent cultivation is a means
of supplying oxygen essential for the more rapid acting aerobic
microbes.
Although the land spreading or fill method for disposal of oily
sludges has been used at some locations, knowledge of the process is
limited to a few trial-and-error applications. An exploratory study
of hydrocarbon decomposition rates was made by the Shell Oil Company
for their disposal area at the Houston, Texas, refinery. Also, spot
samples of their soil were analyzed for microorganism contents by
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Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio. Results of the preliminary hydrocarbon
decomposition rate study and microbial counts were reported by
Dotson, Dean, Kenner, and Cooke.* Sufficient data to permit
evaluation of the process were not obtained and are not available
from other sources. This paper discusses a further study designed
to demonstrate the effectiveness and cost of the soil cultivation
process for disposal of oily waste from petroleum.
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SECTION IV
OILY SLUDGE
Almost all operations of the petroleum industry, including exploring,
producing (extracting), storing, transporting, and refining of crude
oil and the storing, distributing, and handling of products are
potential sources of oily sludges.
Accidental spills of crude oil and petroleum products during the hand-
ling, storing, and transporting operations are the principal cause for
the formation of oily sludges in large quantities. At refineries,
accidents seldom cause oily sludge production. Common sources are
incoming crude oil, ship ballast water, tank and vessel cleanings,
oil-water separators, and numerous miscellaneous sources such as sewer
boxes and emulsion breaking facilities (demulsifier). The quantity of
oily sludge for disposal at a refinery does not depend only upon the
nature of the crude and processing units. Oily sludge formation can
be minimized by prudent operating practices, sensitive attitudes and
suitable control methods. Generally, most of the oily sludges accumu-
late in oil-water separators and in tank bottoms.
Crude oil shipped to the refinery contains emulsified material which is
commonly referred to as bulk, sediment, and water (BS&W). The BS&W
concentration in the crude oil ranges from about 0.01 to 0.1 percent
by volume (%v). This BS&W fraction contains about 307<,v oil, 50%v
water, 10%v carbonaceous matter, and inorganic salts equivalent to
about 10%v. The carbonaceous material which is the part of BS&W that
could eventually become oily sludge for disposal, amounts to about
0.005 percent of the incoming crude oil to the refinery. However, in
the refining steps, much of this carbonaceous material is utilized
into fuels. The quantity of waste sludge from crude oil is small for
the following reasons: 1) Crude oil receipts at a refinery are often
stored in tanks for a few days before being fed to processing units.
During quiescent periods, most of the BS&W material settles out as
tank bottoms and is removed during tank cleanings at three to five-
year intervals. Fortunately, tank bottoms have been in demand for oil
and wax recoveries by independent operators and for road bed additives.
When crude tank bottoms must be handled at the refinery, a concentra-
tion step is possible with conventional slop oil demulsifying
facilities. The BS&W emulsion is broken and some of the carbonaceous
material is included with the recovered oil phase and some with the
water phase. The recovered oil phase is fed to a refining unit and
the water phase flows into an oil-water separator. 2) In the event a
settling time is not possible, the crude oil containing BS&W material
is fed to a crude distilling unit. The BS&W material is removed in
the pretreatment (heater and desalter) section of the distilling unit.
The oil fraction of the BS&W remains in the crude. Water fraction in
the desalter effluent flows into the feedwater stream of an oil-water
separator. Emulsified materials in the oil-water separator will either
-------
enter the recovered oil stream, settle with the bottom sludge inside
the separator box, or remain in the water phase flowing to secondary
treating facilities.
Ship ballast water-handling facilities vary at different refineries as
does the quantity and quality of both the water and oil phases of the
incoming ballast water. At Shell Oil Company's Houston Refinery, bal-
last water from docked ships is pumped into an American Petroleum
Institute (API) design ballast tank, and the water drained from this
ballast tank flows by gravity into a holding pond equipped with down-
stream oil retention baffles and skimmers. Incoming ballast water
sometimes contains oily material which has a density near that of water
and will pass through the ballast tank into the holding pond. If heavy
oil or emulsion material remains in the holding pond for a few days,
the physical characteristics change from a fluid brownish-black mixture
to a thick congealed mass (sometimes greenish in color) which will
float on the water but will not flow. This change apparently is caused
by microorganisms. The congealed mass containing oil may be treated
in a demulsifying unit to recover the oil. If judged to be low in oil.
content, it may become a part of the oily sludge which is a potential
feed for the soil cultivation process. The frequency and quality of
oily waste from the ship ballast water source are uncontrolled and
unknown.
Tank bottoms obtained during cleaning of tanks vary in composition and
the residual oil content can usually be recovered or at least reduced
with emulsion breaking facilities. However, the real bottoms and final
washings from a tank are often oily sludges not suitable for feed to a
demulsifier unit and are potential feed for the soil cultivation pro-
cess.
Oily sludge from oil-water separator and holding pond cleanings is
usually low in oil content and is suitable for disposal by means such
as the cultivation process. The sludge cleanings from the water box
or pond usually contains about two percent carbonaceous material. Oil
box cleanings which are mostly oil can be fed to the demulsifying unit,
but sometimes mixtures of oil, straw, grass, and dirt make this mate-
rial suitable only for disposal.
Solids and oily waste at the demulsifying unit usually accumulate in
tanks which must be cleaned occasionally, and these cleanings cannot
be further improved with additional treatment in demulsification
facilities. Disposal of this oily-sand material can be accomplished
by the soil cultivation process.
Process unit shutdowns include complete cleaning of a piece of equip-
ment and/or vessel before maintenance work begins. In the shutting
down of a process unit, oil is returned to storage. Immediately after
shutdown and where possible, the equipment is washed with water which
removes residual traces of oil and carbonaceous material. This material
is sent to an oil sewer which connects to an oil-water separator.
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SECTION V
PROJECT DESCRIPTION AND OBJECTIVES
The soil cultivation process consists of the treatment of oily waste
material by spreading and cultivating into soil under prevailing
climatic conditions. The project includes three parallel experiments.
Oily feed materials were selected to represent different combinations
of hydrocarbon types. These were designated as sludge A, sludge B,
and sludge C.
Sludge A was a crude oil tank bottoms which contained a natural balance
of hydrocarbon types.
Sludge B was a high molecular weight fuel oil (bunker C or No. 6) con-
taining olefinic and aromatic components.
Sludge C was a waxy raffinate, which is an intermediate waxy oil
product containing highly paraffinic components.
The properties of the three oily materials (simulated sludges) used in
the study are given in Appendix A. Sludge A was added to each of the
three separate soil test plots designated A-l, A-2, and A-3. These
test plots were treated identically except for soil nutrient additions.
A-l was fertilized heavily, A-2 received a moderate or intermediate
quantity of fertilizer material, and A-3 was the control with zero
addition of fertilizer. Sludge B was added to three separate plots
also, and these were designated B-l, B-2, and B-3. Likewise for sludge
C, experimental plots were C-l, C-2, and C-3. Again, the No. 1 plots
were fertilized heavily, No. 2 plots received intermediate quantity of
fertilizers, and No. 3 plots were not fertilized. The design and
details of the project are discussed separately.
Objectives of the project were to determine:
1. The decomposition rate of oily waste sludges in cultivated soil.
2. The effectiveness of adding nutrient supplements.
3. Major microbiological species active in soil where oily wastes
are decomposed.
4. The cost of the process for disposal of oily waste.
5. If the oil infiltrates vertically into the soil at the test site
and the depth of penetration.
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FIGURE 1
DIMENSIONS OF EACH PLOT
WIDTH, FT 12
LENGTH, FT 125
AREA, FT2 1500
DEPTH, FT 0.5
VOLUME, FT3 750
HOLDING
POND
^
/-RAINFALL RUNOFF CONTROL
r
x
• •,
A-l
t
\-2
A- 2
-DITCH
t
J-l
B-2
1
S
B-3
C-l
/
t
C-2
1=
C-3
1
i
A
i-r/
k
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SECTION VI
SOIL TEST PLOTS
Nine soil test plot areas were needed to conduct three parallel experi-
ments with sludges A, B, and C. The layout of plots A-l, A-2, A-3, B-l,
B-2, B-3, C-l, C-2, and C-3 is shown in Figure 1. Each of the nine
plots was 12 feet in width and 125 feet in length (1500 square foot
area). The plots were located near the Houston Ship Channel within the
Shell Oil Company refinery at Deer Park, Texas.
The plots were separated by levees and were designed so that rainfall
runoff from each plot drained through a pipe to a ditch. A plug in the
pipe was used to control the runoff. The levees prevented crossflow of
water from one plot to another and kept oil within the plot area. Ex-
cess runoff water flowed from the ditch into a holding pond (Figure 1)
and was either discharged to the Ship Channel or transferred by vacuum
truck to the refinery biological treating facilities.
Space between the plots permitted tank truck passageway adjacent to
each plot for convenience in spreading oily sludge evenly over the
surface. Also, the plots were cultivated separately. Before moving
from one plot to another, the space between plots was cultivated to
clean the plow and prevent mixing of oil, soil, and fertilizers from
one plot to another.
The experimental plots are located in an area which had been used
previously for oily waste disposal. This offered the advantage of
having a start of oil-consuming variety of microorganisms in the soil
without an acclimation period. However, a disturbing disadvantage as
far as the •experimental work was concerned was the presence of residual
oil in the soil at the start of the experiment. Initial leveling and
grading of the area and preparation of the levees to separate each plot
area are shown in Figure 2. Identification markers were installed as
shown in Figure 3.
The texture of top soil sample from the plot area was 58 percent sand,
14 percent silt, and 28 percent clay. The soil textural classification
was sandy clay loam. At a depth of two feet from the surface, the soil
was classified as loam and at four-foot depth was sand.
The bulk density of oil-free top soil was 1.6 or equivalent to approxi-
mately 100 pounds per cubic foot. The cation exchange capacity at the
start was about 10 milliequivalents per 100 grams (me/lOOg) of soil
and at the end of the experiment ranged from 30 to 60 me/lOOg. (This
increase in exchange capacity is larger than expected from the effects
of adding fertilizers and oil materials. The sample taken at the start
of the project may not have been representative as the samples at the
close of the experiment.) Conductivity was 13 micromhos per centimeter
(Mmhos/cm) at the beginning and ranged from about 4 to 6 Mmhos/cm at
11
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FIGURE 2
PREPARATION OF TEST PLOTS
LEVELING AND GRADING
PREPARATION OF LEVEES TO SEPARATE PLOT AREAS
12
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FIGURE 3
SOIL PLOT IDENTIFICATION MARKERS
••
SIGN AT PROJECT SITE
-
.
,
-
1 • •'• 0 ! • HI • • - • •
I .
:- . — --.p>
IDENTIFICATION MARKER FOR EACH PLOT
13
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the close of the study. Conductivity measurements were made at room
temperature (20-22°C). Other properties (including pH, oil, nitrogen,
phosphorus, sulfur and metals contents) of the soil at the beginning
of the project are tabulated and discussed along with results of the
study.
14
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SECTION VII
SOIL NUTRIENTS (FERTILIZER)
Since the disposal of oily waste by the soil cultivation process depends
upon the soil microorganisms to oxidize the oils or convert the oily
waste into cell protoplasm, the ingredients needed for microbial growth
must be present. The main elements are carbon, hydrogen, oxygen,
nitrogen, potassium, and phosphorus. Also, key trace elements includ-
ing sulfur, sodium, calcium, magnesium, iron, and others are needed.
Most of the trace elements are abundant in soils, but two of the main
elements, nitrogen and phosphorus, often limit organic cellular growth.
Chemical analyses of protoplasm indicate phosphorus requirement is
about one-fifth the nitrogen requirement.1*
In agricultural crop production, nitrogen and phosphorus are removed
from the soil with the harvested grain or forage. Replenishing of the
nutrients is required. For a waste disposal system such as the soil
cultivation process, there should be an equilibrium condition estab-
lished which would minimize the need for supplementing the nutrients.
Endogenous metabolism, autoxidation of cellular protoplasm, results in
the release of nitrogen and phosphorus previously used for synthesis.
The released nutrients are made available for reuse in biological waste
treatment systems.1* No reference information was found to use as a
guide in selection of appropriate quantities of nitrogen and phosphorus
which should be added to the biological system. Instead, the selection
of fertilizer quantities was based upon agricultural-oriented expe-
rience. Grass land is frequently fertilized with 500 pounds of
nitrogen and 100 pounds of phosphorus per acre, and three times these
quantities have been used according to our consultants. Warnings that
1) excess nitrogen fertilizer elements hinder (poison) bacterial action
and 2) excessive total soluble salts may cause unfavorable osmotic
conditions for bacterial growth, were considered in the selection of
the quantities of nutrient additive. Excess phosphate was not con-
sidered toxic except for its contribution to the total soluble salt
content. Initial additions in pounds per acre (Ibs/ac) of nitrogen
(urea) as N were 1000, 500, and zero to plots 1, 2, and 3, respectively.
The additions of phosphorus (calcium hydrogen phosphate) were 200, 100,
and zero Ibs/ac as P20s to plots 1, 2, and 3, respectively.
Periodic analyses of nitrogen and phosphorus were made, and additional
fertilizer materials were added to plots 1 and 2 during the course of
the experiment. The types and quantities of fertilizer materials
added during the study are shown in Table 1.
15
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TABLE 1
NUTRIENTS ADDED DURING THE STUDY
(The Number 3 Plots Were Not Fertilized)
1970
FERTILIZER
Urea, as N
Ammonium
Nitrate, as N
RATIO
N-P-K
45-0-0
35-0-0
Phosphorus,
as P00C 0-46-0
Potash, as K-0 0-0-60
Ib/plot
Ib/acre
ppm by wt
Ib/plot
Ib/acre
ppm by wt
Ib/plot
Ib/acre
ppm by wt
Ib/plot
Ib/acre
ppm by wt
MAY 7
PLOTS NO.
1 2
34 17
1000 500
450 225
7 3.5
200 100
95 47
AUGUST 7
PLOTS NO
1
58
1700
775
184
5350
2450
.
2
23
680
305
46
1340
610
1971
JAN. 27
PLOTS NO.
APRIL 21
PLOTS NO.
AUGUST 11
PLOTS NO.
35
1000
470
17
500
225
9
260
120
4.5
130
60
12
350
160
6
175
80
30
875
400
15
438
200
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SECTION VIII
STARTUP, OPERATION, AND APPEARANCE
After the plots had been laid out and the levees prepared, each plot
was cultivated with a "roto-tiller" type plow. Fertilizer materials
were added by manually spreading the solid granular fertilizer over
the surface of plots No. 1 and 2. After spreading fertilizer and be-
fore adding oily sludge materials, the plots were cultivated a second
time to mix and distribute the fertilizer salts with the soil.
Simulated oily sludges were transported to the test plot area with a
vacuum tank truck, and the sludge was distributed over the surface of
the soil by manual direction of a discharge hose attached to the tank.
Soil cultivation and addition of oil are shown in Figure 4. Mixing of
the oil and the soil by cultivation appeared uniform and presented no
problem at the ambient May temperature of about 80°F.
The initial schedule for cultivating the soil plots was once each two
weeks, weather permitting. However, after the first quarter, the plow-
ing frequency was increased in an attempt to improve oil decomposition
rates. The plowing frequencies and results are discussed separately.
After about six months of cultivation, the soil was friable, had lost
the oily appearance, and was judged from test results to be suitable
for a second addition of the oily sludge. Some differences in the
plots were obvious. For instance, the color of the No. 3 plots was
darker than that for Nos. 1 and 2. Photographs of these plots just
before and just after the addition of the second application of the
simulated oily sludges are shown for the "A" plots in Figure 5, for
the "B" plots in Figure 6, and for the "C" piots in Fig'ure 7. The
date for this second" addition of sludge was in early February, and
the temperature was in the low 40's F. Congealing and solidification
of the sludges were apparent, and mixing of the viscous oily matter
into the soil was not successful until the ambient temperature had
increased to about 80°F.
At the close of the 18-month experiment, the soil had again returned
to a friable condition with the appearance of a normal agricultural
soil. A close-up view of soil in plots A-l, B-l, and C-l is shown in
Figure 8.
Although no attempt was made to grow vegetation matter on soils
previously used for oil decomposition during this experiment, native
grass and plants did sprout and grow on top of the levee. The soil
in the levees was the same as the starting test plots, which contained
about ten percent oily material as discussed later.
17
-------
FIGURE 4
SOIL CULTIVATION AND ADDITION OF OIL
18
-------
FIGURE 5
BEFORE AND AFTER SECOND ADDITION OF OIL TO "A" PLOTS
19
-------
FIGURE 6
BEFORE AND AFTER SECOND ADDITION OF OIL TO "B" PLOTS
20
-------
FIGURE 7
BEFORE AND AFTER SECOND ADDITION OF OIL TO "C" PLOTS
21
-------
FIGURE 8
:;; - /> '-^vl^^V'V*«*ivl\.v^-'^'^'"?-v'>:'','';r.. ^•:M&''^L;'*r« '•
%•-... .\>< •' v -iT***-'' »<*- ' i. ''•*'.. ,":?•:_: •:'• \- *.•*.-•:•''< -.,•' . *?,-^
:** • -fc . \ . . *W'-ti» - .vK*--* v 4 . ' ^- .. •. l.i£. •'--•. t*M^S.\*W **»...•• .. - . . -*-.*;
•:V !, %*j£.i
W$* :^i
• rr'/'atf'-'t'*., .,v;. " ••• . ;..f
•-,,-'-'-'>f ^^^CfrSWWX^S&W^ '•"• '• -^3^". -''- 'i- -" i'./**i •' " '• ''•'
'- v' ;
.,••
^ -•- • • ••-
SOIL AT END OF THE DEMONSTRATION PERIOD
22
-------
SECTION IX
SAMPLING AND TESTING
Oil and nutrient contents were used as controls for the experimental
work during the 18-month project, and these components were tested
frequently. (Microbiological analyses, hydrocarbon types of oil added
to and extracted from the soil and the oil content of soil core samples
at depths up to six feet were made to achieve the project objectives.
Also, metals, nitrogen, phosphorus, and sulfur contents of the soil
and infrared absorption and gas chromatography of extracted oils were
examined.) The samples for analyses, analytical tests, method
references, and the frequency of tests during the experimental period
are summarized in Table 2. In addition, moisture, pH and temperature
of the soil were measured on a regular basis. Moisture contents of
the soil were obtained along with the oil content determinations as
described in Appendix E. Temperature and pH were measured using
mercury thermometers and a glass-calomel electrode meter. The soluble
nutrients were dissolved from oil-free soil (after CCli^ extraction)
using distilled deionized water for nitrogen and 1.4 normal (1.4 N)
ammonium acetate (NH^Ac) in hydrochloric acid (HCl), pH 4.2, for
phosphorus (P), sodium (Na), potassium (K), magnesium (Mg) and calcium
(Ca), according to the procedure recommended by State Soil Testing
Laboratories publication.^ For the less soluble metals, zinc (Zn),
manganese (Mn), copper (Cu), iron (Fe), and lead (Pb), a 50/50 mixture
of concentrated HCl and concentrated nitric acid (HN03) was used for
the extraction solvent. Analyses of the solutions were by atomic ab-
sorption. The soil consultant used 1.0 N NHi|Ac at pH 7 for extracting
P, K, Na, Ca, and Mg, and 0.1 N HCl for extracting Zn, Mn, Cu, and Fe.
These latter extraction solvents are generally considered a good
measure of the quantities of elements available for growth of plant
life. Rainfall runoff water was tested for oil and nutrient contents.
The method used for oil in water determinations was American Petroleum
Institute (API) method 731.llt Oxygen determinations of the soil,
although desirable, were not made because a suitable method was not
available.
The obtaining of a representative soil sample was a recognized problem
from the start of the project. Although cultivation mixed the surface
soil vertically, complete horizontal and vertical mixing throughout a
test plot was not attained. In an effort to minimize inconsistencies,
samples were taken immediately after cultivation and from several loca-
tions, then composited before submitting for tests. The sampling
procedure included combining portions of soil from three sampling
points to form subsamples a, b, and c, as shown in Figure 9. Each
subsample was analyzed separately for oil content, and the resulting
data for the 18-month experimental period are given in Appendix A.
For all other tests, including nutrients, microbial and metals con-
tents, and other properties of the soil, subsamples a, b, and c were
23
-------
TABLE 2
SAMPLING AND TESTING FREQUENCY
Sample
Soil, top 6 inches
to
Soil core, 2, A, & 6 ft.
Oil extracted from soil
Oil added to soil
Analytical Test
Oil content
Nutrients (NH3, NO,,
P205)
Total nitrogen, phos-
phorus and sulfur
Microbial content
Metals
Oil content
Nutrients (NH,, NO,,
P2o5)
Hydrocarbon type
Infrared spectroscopy
Gas chromatography
Physical properties
Metals
Hydrocarbon type
Total nitrogen, phos-
phorus and sulfur
Infrared spectroscopy
Gas chromatograph
Reference
Appendix E
8
5,10
Standard methods
Specific methods11'12'13
Appendix B
Atomic absorption
8
Appendix E
Standard methods '
ASTM D-20079
Appendix D
Shell Oil Co.7
ASTM methods
Emission Spectroscopy
ASTM D-20079
Specific methods
Appendix D
Shell Oil Co.'
11,12,13
Approximate Frequency
Bi-weekly
Monthly or bi-weekly
if needed
Beginning and end
Monthly
Beginning, midway, and end
Beginning, midway, and end
Midway and end
Beginning, midway, and end
Beginning, midway, and end
Beginning and end
Beginning
Beginning
When added
Beginning
Beginning
Beginning
-------
FIGURE 9
o o o
000
o o o
TEST PLOT 125 FT. X 12 FT.
PORTIONS FROM THREE SAMPLING
POINTS WERE COMPOSITED TO
FORM EACH SUB SAMPLE
SUB SAMPLE c
SUB SAMPLE b
SUB SAMPLE a
TYPICAL SAMPLING POINTS
25
-------
composited to represent the whole test plot. For example, A-l soil
sample was a composite of A-la, A-lb, and A-lc subsamples.
Analytical results are given in Appendices A, B, C, and D.
26
-------
SECTION X
EFFECTIVENESS OF THE SOIL CULTIVATION PROCESS
Oil Decomposition Rate and Effect of Fertilizer
Percent weight oil in each soil plot given in Tables 5, 6, and 7 of
Appendix A are shown graphically related with time in Figures 10, 11,
and 12. Residual oil of about ten percent in the soil was due to
previous use of the'soil area for oily waste disposal as mentioned
earlier. The increased quantities of oil in all plots for May 1970
and February 1971 were due to the addition of oil to the soil. Devia-
tion in the oil content data from the linear relationships shown on
each of the figures may indicate more rapid reaction during some
periods than others but is likely due to nonrepresentative samples.
The straight line relationship was calculated by the method of least
squares. For the "B" plots, Figure 11, inconsistent data during
February to April, 1971, were due to the inability to mix the highly
viscous oil into cool soil with the roto-tiller type cultivator.
Generally and as shown in each of Figures 10, 11, and 12, from the
first addition of oil in May 1970 to about November 1970, the oil con-
tent of the soil decreased markedly. During the period November 1970
to February 1971, a reduction of oil was not apparent. From February,
when a second dosage of oil was added, to October 1971, the oil content
again decreased. The reason (or reasons) for the period of inactivity
is not clearly evident. During this period, food supply may have been
limiting because the concentration of oil in the soil was in some cases
near the starting content, and this residual oil may be nonreactive or
slowly reactive with soil microorganisms. Another reason may have
been the lack of available nutrients which ranged from about 10 to 50
ppm ammonia as N during this period. A third reason may have been
temperatures that were too low for favorable bacterial growth.
The soluble nitrogen (N) and phosphorus (as P205) contents from Table 5
of Appendix A for the "A" plots during the project are shown in Figures
13, 14, and 15. The trend of these nutrient data for the "B" and "C"
plots is similar and is not shown graphically. Urea was used as the
nitrogen nutrient at the start of the project as recommended by a soil
consultant. The reason for selecting urea was to avoid increasing the
salt content of the soil. Immediately after fertilizing in May 1970
(Figure 13), the ammonia (NHs) content was about 700 ppm by weight as
N in the soil. This was likely due to inadequate mixing or non-
representative sample because the theoretical amount added was about
460 ppm as N (Table 1). The concentration rapidly decreased to about
30 ppm as N during June and to zero in July. A larger dosage was
added in August causing the NHs concentration to reach about 1500 ppm
as N. During September and October, the NHs content remained about
500 ppm as N. During this same period, the nitrate (NOs) content was
zero and ammonia was being lost to the atmosphere. The odor of ammonia
27
-------
20
10
o
t/0
5
20
O
DC:
20
10
A
FIGURE 10
A-l
Jan. Feb. Hir. Apr. Niy June July Aug. Sept. Oct. Nov. Dec. Jin. Feb. Kir. Apr. May June July Aug. Sept. Oct. Nov. Dec.
TEAR OF 1970 »EA8 OF 1971
OIL CONTENT OF SOIL
'A" PLOTS
28
-------
FIGURE 11
30
20
10
o
oo
z 30
>—i OO
•—I
_J 00
5 co 20
C5 O
i—i OO
a:
i— Q
10
30
20
10 '
Jan. Feb. Mir. Apr. Kty June July Aug. Sept. Oct. Nov. Dec. J«n. Feb. Kjr. Apr. tajr June July Auq. Sept. Oct. Nov. Dec
TEAR OF 1970 TEAR OF 1971
OIL CONTENT OF SOIL
•B" PLOTS
29
-------
2C
10
o
1/1
20
10
o:
LU
a.
20
10
FIGURE 12
A A
Jan. Fel). Mar. Apr. Hiy June July »U9. Sept. Oct. Nov. Dec. Jan. Feb. Kjr. Apr. Hsy June July Aug. Sept. Oct. Nov. Dec.
YEAR OF 1970 »EAR OF 1971
OIL CONTENT OF SOIL
'C" PLOTS
30
-------
FIGURE 13
lOOOr
IT)
Q.
Q.
O
O
200.
PLOT A-l
Dec. Jin. Feb. Mar. Apr. Kay June July Aug. Sept. Oct. Nov. Dec. Jin. Feb. Kir. Apr. Hay June July Aug. Sept. Oct. Nov. Dec
TEAR OF 1»70 VEAR OF 1971
NITROGEN CONTENT OF SOIL
PLOT A-l
31
-------
1000
800
600
o.
CL
C5
O
o:
« 400
200
FIGURE 14
PLOT A-2
Dec. J«n. Frt. Kir. Apr. Miy June July Aug. Sept. Oct. Nov. Dec. Jan. Fib. Kir. Apr. M«y June July Aug. Sept. Oct. Nov. Dec.
TEA* OF 1970 YEAR OF U71
NITROGEN CONTENT OF SOIL
PLOT A-2
32
-------
FIGURE 15
lOOOr
800
o
-------
was strong in the test plot area during cultivation periods. When this
was observed, the frequency of cultivations was increased from once per
two weeks to once per week or more (Appendix A, Table 5). The next
addition was in January 1971, and ammonium nitrate (NH* NC>3) was used
instead of urea since the presence of nitrate was desirable according
to our microbiology consultant. Also, a dosage of potash was recom-
mended and added at this time to eliminate the possibility of a
potassium deficiency. The use of NH^NC^ and relatively small dosages
applied more frequently (about once per three months) was practiced
for the remainder of the experiment. The lower concentrations of NHg
for the No. 2 plot shown in Figure 14 did not emit a detectable odor,
but the cultivation frequency was the same for all test plots including
the unfertilized No. 3 plot. Soluble phosphorus (phosphate expressed
as P20s) contents of the soil, shown in Figure 15, did not appear to
be a limiting factor. During June and July 1970, the test plots
treated with bunker C (No. 6) fuel oil appeared to be repelling water.
Exploratory tests indicated additional phosphorus fertilizer improved
the wetting characteristic of the oily soil. Again, with the advice
of a consultant, relatively large quantities (2500 ppm as ^2^5 to tne
No. 1 plots and 600 ppm as T?2®5 to tne No. 2 plots) of phosphorus
fertilizer were added. Differences in oil decomposition rates for the
No. 1 and No. 2 plots are likely due to the fluctuating nitrogen con-
tents rather than to the relatively constant phosphorus concentrations.
The effects of fertilizer on the oil decomposition rate as related with
temperature are shown in Figures 16, 17, and 18 for plots "A", "B", and
"C", respectively.
The pounds of oil removed per cubic foot of soil (based upon a soil
weight of 100 lbs/ft3) during the project are shown to be about 15
pounds for A-l and A-2, which had been fertilized, and about 10 pounds
for the A-3 plot which was not fertilized (Figure 16). Oil removal
rates for the "B" plots (Figure 17) were about 25, 20, and 12 lbs/ft3
of soil for B-l, B-2, and B-3, respectively, and for the "C" plots
(Figure 18) were about 25, 20, and 10 lbs/ft3 for C-l, C-2, and C-3,
respectively. These data indicate a direct relationship between the
quantity of fertilizer added and oil removal rate. Each of these
plots show the oil removal rate to be minimal during the winter months
when the temperature was below about 70°F (20°C). However, as dis-
cussed earlier, the concentration of oil in the soil was near the
starting oil content during this same period, and the apparent effect
of temperature may have been coincidental.
The oil decomposition rate expressed in pounds of oil per month per
cubic foot of soil are given in Table 3. The decomposition rate for
the periods May to November 1970, and February to October 1971,
averaged 0.90, 0.94, and 0.71 lbs/ft3/mo for A-l, A-2, and A-3; 1.79,
1.67, and 0.83 lbs/ft3/mo for B-l, B-2, and B-3; and 1.73, 1.25, and
0.67 lbs/ft3/mo for C-l, C-2, and C-3, respectively. For the three-
month period of November 1970 to February 1971, the oil decomposition
rate was minimum. The average decomposition rate per year at these
34
-------
FIGURE 16
LU
35
30
25
20
15
10
90
80
70
60
50
LEGEND:
A-2 x x
A-3 A—-A
AMBIENT •
Q o
UJ 10
LU
O
Apr. H«jr June July Au?. Sept. Oct. Nov. D«. Jan. Feb. Kar. Apr. Hay June July Au9 Seot. Oct. "iov Dec
TEM OF 1970
TEAR OF 1971
TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP
II AH
A" PLOTS
35
-------
FIGURE 17
°c
35
30
25
20
15
10
90
80
70
60
50.
Q o
UJ 00
UJ
O co
20
10
'"
0
LEGEND:
B-l .—
B-2 X—
B-3 A—
AMBIENT I
—x
--&
Apr. mj June July Aug. Sept. Oct. No». Dec. Jan. Feb. Kar. «pr. HJy June July Aug. Seot. Oct. Hoi. Dec
TIM OF 1)70 TUR OF 1971
TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP
"B" PLOTS
36
-------
FIGURE 18
UJ
Q.
°c
36
30
25
20
15
10
90
80
70
60
50.
LEGEND:
C-l •—
C-2 x—
C-3 A—
AMBIENT
o
(75
£ °
0£. m
2°
10
0
•or. my June July Aug. Sect. Oct. Nov. Dec. Jin. Feb **r. »pr. Kay Jun« July «u9. Sect. Oct. lo» On
n« or
run OF
TEMPERATURE-DECOMPOSITION RATE RELATIONSHIP
"C" PLOTS
37
-------
TABLE 3
OIL DECOMPOSITION RATE
POUNDS OF OIL PER MONTH PER CUBIC FOOT OF SOIL
Plot
A-l
A-2
A-3
B-l
B-2
B-3
C-l
C-2
C-3
1
2
3
May to
Nov. 1970
0.67
0.50
0.17
1.83
1.83
1.16
1.83
1.50
0.83
Feb. to
Oct. 1971
1.12
1.37
1.25
1.75
1.50
0.5
1.62
1.0
0.50
Average
0.90
0.94
0.71
1.79
1.67
0.83
1.73
1.25
0.67
Nov. 1970
to
Feb. 1971
Minimum
Minimum
Minimum
Minimum
Minimum
Minimum
Minimum
Minimum
Minimum
Average
Per Year
0.67
0.70
0.53
1.34
1.25
0.62
1.30
0.94
0.50
1.10
0.96
0.55
38
-------
test conditions was 1.10, 0.96, and 0.5 Ibs/ft3/mo for heavily ferti-
lized No. 1, medium fertilized No. 2, and unfertilized No. 3 plots,
respectively. Therefore, fertilization with the medium quantity added
to the No. 2 plots increased the oil decomposition rate about 75 per-
cent over the unfertilized No. 3 plots, and the larger quantity of
fertilizer added to the No. 1 plots increased the oil decomposition
rate 100 percent. Variations in the effect of fertilizer are apparent.
For the "A" plots during the period February to October 1971, the oil
decomposition rate for the No. 2 and No. 3 plots exceeded the reduction
for the No. 1 plot, indicating the fertilizer addition to the No. 1
plot was excessive. Also, for the "B" plots during the period May to
November 1970, the oil removal rate for the No. 2 plot was the same as
for the No. 1 plot, indicating the additional fertilizer applied to
No. 1 plot was not needed. An optimum fertilization program would
appear to be 1) addition of slightly excess quantities of phosphorus
and potassium, on a one-time basis, and 2) the addition of nitrogen in
the form of ammonium nitrate in small dosages as needed based upon
tests to maintain a positive (10 to 50 ppm) NH3 and/or N03 content.
Metals Contents of Soils
Metals obtained with different soil extracting solvents, total nitrogen,
total sulfur, and total phosphorus are given in Tables 8, 9, and 10 of
Appendix A for the "A", "B", and "C" plots, respectively. The data
show inconsistencies and real effects of the metal components are not
apparent. Copper, zinc, and lead are normally considered to exhibit
harmful effects on biological growth. These elements may have been
insoluble at soil pH conditions and not available to the microorganisms.
Oil and Nutrient Infiltration
Oil and nutrient concentrations at depths of 2, 4, and 6 feet (Table 11
of Appendix A) show these constituents did not infiltrate the soil under
the conditions of the project. As discussed earlier, oil was present
at the two-foot depth at the start of the study, and no change was
noted after 18 months. The presence of phosphate at the two-foot depth
was expected since the initial grading and leveling operations mixed
the top two feet of soil.
39
-------
TABLE 4
QUANTITY AND COST BASED UPON EXPERIMENTAL CONDITIONS
Calculations For Sludge Containing 100 Percent Oil;
OIL DECOMPOSED/MONTH
POUNDS/CUB1C FOOT
POUNDS/SQUARE FOOT
POUNDS/ACRE
GALLONS/ACRE
BARRELS/ACRE
SPREADING COST/ACRE
FERTILIZER
NITROGEN, POUNDS/YEAR
COST/POUND
COST/MONTH
PHOSPHORUS, POUNDS/YEAR
COST/POUND
COST/MONTH
SPREADING COST/ACRE
CULTIVATION, HOURS/PLOWING
COST/HOUR
COST/2 PLOWINGS
QUANTITY DOLLARS
1
0.5
21,780
2,904
69.14
70.00
1,000
500
0.15
12.50
0.145
6.00
60.00
25.00
TOTAL DOLLARS
PER PER
MONTH BARREL
70.00
12.50
6.00
5.00
400.00
493.50
7.15
Calculations For Sludge Containing 33 Percent Oil:
DECOMPOSED/MONTH
BARRELS/ACRE
SPREADING COST/ACRE
FERTILIZER
MATERIAL AND SPREADING
(SAME AS ABOVE)
CULTIVATION
(SAME AS ABOVE)
COST/2 PLOWINGS
210
210.00
210.00
23.50
4.00. QQ
633.50 3.00
40
-------
SECTION XI
QUANTITY AND COST BASED UPON CONDITIONS
DURING THE PROJECT
The pounds of oil decomposed per cubic foot of soil per month from
Table 3 were 1.10, 0.96, and 0.55 for the Nos. 1, 2, and 3 plots,
respectively. A quantity of 1.0 Ib/ft3/mo was selected as the basis
for determining cost of the process. The fertilizer requirement was
assumed to be 1,000 pounds of nitrogen and 500 pounds of phosphorus
per acre per year, and costs for spreading oil and fertilizer and
cultivating the soil were based upon the expense incurred during the
project period. The quantities and costs based on experimental condi-
tions are given in Table 4. An oil decomposition rate of 1 Ib/ft3/mo
is equal to 21,780 Ibs/acre/mo or about 70 bbls/acre/mo. The cost for
delivering the oil to the area and distributing the oil over the
surface of the soil was about $l/bbl and for 70 bbls/acre/mo would
cost $70/acre/mo. The fertilizer material and labor for spreading
costs prorated on a monthly basis was estimated to be about $23.50/mo.
Cultivation would require about 8 hrs/acre at $25.00/hr and two
plowings/mo totals $400.00/mo. The total cost/acre/mo was estimated
to be $493.50 or about $7.15 per barrel of oil. On a basis of oily
sludge which may contain 33 percent oil, the total volume to be
delivered and spread would be 210 barrels and would cost $210 instead
of $70 for 100 percent oil. The cost for disposal of oily sludge
would be about $3.00 per barrel.
41
-------
FIGURE 19
LEGEND:
A-l •-
A-2 x-
A-3 A
Apr. Hiy June July Aug. Sept. Oct. Nov. Dec. Jin. Fee. Kir. Apr. M«y June July Aug. Sept. Oct. Nov. Dec.
TEAR OF 1970 YEAR OF 1971
MICROBIAL CONTENT OF SOIL FROM "A" PLOTS
42
-------
SECTION XII
MICROBIAL ACTION
A natural function of microorganisms found abundantly in soil is to
decompose nitrogenous and carbonaceous materials into microbial cellu-
lar matter. Side products of gases and partially reacted organics
("humus") are formed. When oil or hydrocarbon is the only source of
carbon, oil degrading microorganisms survive and become the predominant
species. An intermediate product is organic acids as discussed later.
Results of monthly determinations of the predominant organisms and a
brief description from literature of individual organisms are given in
Appendix B.
Due to mixing of various depths of soil in the initial grading and
leveling operations, the microbial population was different on all
plots. However, the microbial population contained oil decomposing
bacteria especially of the Flavobacterium and Pseudomonas species.
During the project period, distribution of the microorganism species
was not greatly different as shown in Tables 1, 2, and 3 of Appendix B
for the three oils used in the experiment. During the first eight
months, the Flavobacterium, Nocardia, Pseudomonas, and Arthrobacter
appeared to be most prominent in all plots. During the last nine
months, Corynebacterium increased in prominence and Arthrobacter was
seldom a prominent species. Also, during the latter.part of the ex-
periment, yeast was found prominent in numerous samples. The addition
of fertilizer did not appear to materially affect the distribution of
microorganisms but did affect the total aerobic count. The total
aerobic count for "A", "B", and "C" plots are given in Tables 5, 6,
and 7 of Appendix A and shown graphically in Figures 19, 20, and 21.
The No. 1 plots (heavily fertilized) generally were higher in total
aerobic count than No. 2 (medium fertilized) and No. 3 (not fertilized)
plots. Also, the addition of oil in May 1970 and February 1971
appeared to upset the soil microbial equilibrium and caused the total
aerobic count to be low.
An exploratory experiment was made to determine the effect of adding
oil (same as used on a specific test plot during the project period)
to the nutrient agar used in the microbial analyses. The primary
effect appeared to be a lower total cell count for the oil containing
agar. Data from this exploratory test, plus summarized data and com-
ments by the consultant concerning the microbial analyses of the total
project period, are given in Appendix C.
43
-------
FIGURE 20
200
180
160
140
x 120
co
UJ
CQ
100
80
60
40
20
LEGEND:
B-l •
B-2 x--
B-3
X
— -A
Apr. Miy June July Aug. Sept. Oct. Nov. Dec. Jan. Feb. Kir. Apr. May June July Aug. Sept. Oct. Nov. Dec.
YEAR Of 1970 YEAR OF 1971
MICROBIAL CONTENT OF SOIL FROM "B" PLOTS
44
-------
FIGURE 21
200
180
160
140
o
x 120
CO
§ 100
80
60
40
20
LEGEND:
01 -
C-2 x-
C-3 A A
Apr. Hay June July Aug. Sept. Oct. Nov. Dec. Jan. Feb. Kir. Apr. Hay June July Aug. Sept, Oct. Nov. Dec.
YEAR OF 1970 • YEAR OF 1971
MICROBIAL CONTENT OF SOIL FROM "C" PLOTS
45
-------
FIGURE 22
30
A-l
LEGEND:
SATURATES S
RESINS R
AROMATICS A
UJ
Q_
20
IU
S
R
A
S
R
A
—.^^
~~"~~-^. ^
^~~~~~~~- —
—
-
S
A
~~^^
— — — _
.
••*.
^^
— -~-^T~I
A-2
30
20
10
n
S
.B
A
S
R
A
^ -«^ ^^
' — •
S
R
A
^
— — __
^^-^^
•—i
_
—
^
__ "^^.
~~"~~
^^
-~
-
30
A-3
20
10
n
Dec. Jan. Feb. Har. Apr.
s
o
K
A
"•>
S
R
A
Ju
~
~- — — — _
-------
SECTION XIII
COMPOSITION OF OIL EXTRACTED FROM THE SOIL
Oils added to and extracted from soil plots were 1) quantitatively
analyzed by a clay gel adsorption method9 for hydrocarbon types (total
saturates, resins, and aromatics); 2) qualitatively analyzed by infra-
red absorption for "fingerprinting" differences in oils from the
various test plots; and 3) qualitatively analyzed by gas chromatography
for retention times relative to normal paraffin carbon numbers. Also,
the gas chromatography method7 was used to obtain a boiling point pro-
file (up to about 510°C) relative to percent weight of the oil.
HYDROCARBON TYPES
The clay gel method9 utilizes clay to retain the strongly polar con-
stituents (asphaltenes, organic acids, etc.) and designates them as
resins. Silica gel is then used to separate the saturate and aromatic
fractions. Hydrocarbon types from Tables 12, 13, and 14 of Appendix A
are related with time and shown in Figures 22, 23, and 24 for Plots
"A", "B", and "C", respectively. For the "A" plots which were treated
with crude oil tank bottoms, the saturate and aromatic contents de-
creased and the resin content increased, indicating a conversion of
saturates and/or aromatics to resinous material. The magnitude of the
change appeared greatest for the No. 1 plot and least for the No. 3
plot. The change for No. 2 plot was intermediate between A-l and A-3,
indicating an effect of added fertilizer material. For the "B" plots
which were treated with bunker C fuel oil, the saturate and aromatic
contents decreased and the resin content appeared to remain unchanged,
possibly indicating a relatively nonreactive resinous fraction. The
magnitude of change for B-l and B-2 (Figure 23) appeared to be about
the same and B-3 showed the least reaction. For the "C" plots which
were treated with waxy raffinate, the saturate content decreased with
time, the resin content appeared to increase slightly, and the aromatic
content was not markedly changed, substantiating the fact that paraf-
fins react more easily than aromatics. The three figures (22, 23, and
24) indicate more rapid changes in composition for No. 1 and No. 2
plots which were fertilized than for the No. 3 plot. Further differ-
ences in the oils from fertilized and unfertilized plots were evident
from infrared and gas chromatography examinations.
INFRARED SPECTROSCOPY
The infrared (IR) method for analyses of the oils extracted from the
soil and a discussion of the analysis are given in Appendix D. The IR
spectra of oil extracted from the soil after eight months and after 17
months of the project are given in Figures 25, 26, and 27 for "A", "B",
and "C" plots, respectively. These figures are discussed separately
in Appendix D. General conclusions from the study are as follows:
47
-------
FIGURE 23
CJ3
Ul
LEGEND:
MES S
R
B-1
30
i A
:0
o F
R
A
S
R
— *
A
-*•>.
--^.. ^
^^^-
—
B-2
0
0
0 Is
T?
A
n 1 1
-
S
R
A
^*\.
^>>
-»» «>^
~^"~--~ -^^
S
R
A
S
R
—
A
"\^
"^
"""-•
^-
'
^^_
• — ,
—
3MIUKMI LO
RESINS
^ AROMATICS
\
\
^ -v.
">""^-
\^
--^_
"^--^,
B-3
0
0
o [s
I
A
n LJ
S
R
—
A
^-^^^
~~*' — ^^_ ^*~
~~~~~— --~.___^
^™
S
R
A
~-— ^
^^™
•""
^^~^-
^ — — ~
—
—
—
Jan. Fed M«r. Apr. K»y June July Aug. Sept. Oct. Nov Dec. Jan Feb. fir. Apr. fiy June July Aug. Sept. Oct. Nov. Dec
YEAR OF 1970 "EAR OF 1971
HYDROCARBON TYPE FOR "B" PLOTS
48
-------
30
20
10
30
20
o 10
30
FIGURE 24
C-l
LEGEND:
SATURATES S
RESINS R
AROMATICS A
S
R
IX
A
S
E
A
*\
""^
• —
^^
S
R
A
-^
^\
•-.
\
^\
\
— .. „__
J\
C-2
s
R
A
— 1
S
R
A
-^.
•>«.
^-^^
^"
^^ ^™
-
S
R
A
^
^•^
.__
C-3
20
10
Dec. Jan. Feb. Mar. Apr.
R
A
Hay
S
R
A
Ju
~~~— — — .
ne July Aug. Sept. Oct. Nov. Dec.
Ji
n. Fe
S
R
A
b.
~ ~-
Par. Apr. Hay
Ju
^~~-- •-,
ne July Aug. Sept
0
t. Nov. Oe
HYDROCARBON TYPE FOR "C" PLOTS
49
-------
4000 3000 3000
9 10 II 12 11 14 \f
HOOfRATf
IKFRARED SPECTRA OF OILS EXTRACTED FROM "A" PLOTS
(SOILS TREATED WITH CRUDE OIL TANK BOTTOHS)
Smple: 8.5 to 15.0 "Icronj - 10J«/v CS? Solution
2.0 to 9.0 nUrons - 4lw/v CC14 Solution
Reference: Solvent Covpenuted
Cell TMcknesi: O.S m. Hid
AFTER 8 MOUTHS
1500 CM' 1000 900 BOO
WAVELENGTH (MICRONS,
9 10 II 12 13 U 1?
-------
4000 3000 2000 1500
INFRARED SPECTRA OF OILS EXTRACTED FROM "B" PLOTS
(SOILS TREATED WITH BUNKER C FUEL OIL)
Sample: 8.5 to 15.0 microns - lOWv CS? Solution
2.0 to 9.0 microns - 4:w/v CCU Solution
Reference: Solvent Compensjteo
Cell Thickness: O.S ran,
-------
Ln
FERTILIZATION
INFRARED SPECTRA OF OILS EXTRACTED FBOH T PLOTS
(SOILS TREATED KITH K/UY RAFFIKATE)
Suvle: 8.5 to 1S.O nicrons - lOU/v CS2 Solution
2.0 to 9.0 ilcrms - 4lw/v CCU Solution
Reference: Solvent Covpensited
Cell Thickness: 01 m. Hid
ftnCR 8 MOUTHS
1500 CM' 1000 900
WAveiENGTH (MICRONS'.
10 II
WAVELENGTH (MICRONS!
-------
The IR spectral character of all the oils extracted from the soil plots
are similar to that of the oil found in the soil at the beginning of
the study, despite a substantial variation in the type of oils added to
the soil. The extracted materials would be grossly characterized from
the IR spectra as highly aromatic oils containing a substantial amount
of condensed multi-ring aromatic structures. Organic acids were
present in each of the extracted oil samples, but in varying amounts,
based upon the presence of an acid carbonyl (C=0) group (absorbing at
5.85y). The oils from plots that were fertilized show higher concen-
trations of organic acids, and the concentration appeared to be the
greatest in the heavily fertilized plots. The increase in organic
acids correlates, in general, with a decrease in the long chain paraf-
fin (absorption at 13.88y) and a decrease in total saturate groups
(absorption at 6.86y and 7.25y). A substantial reduction of long chain
paraffin groups was observed even in the absence of fertilizer suggest-
ing that such groups are the most readily decomposed under the condi-
tions existing in these studies.
GAS CHROMATOGRAPHY
Gas chromatographs7 were obtained with nonpolar media which presumably
makes no separation according to molecular type and permits passage of
all hydrocarbon components on the basis of their boiling points. The
retention times and boiling points of normal paraffins were used as a
basis for determining temperatures. The detector response of a sample
being analyzed indicates the quantity of hydrocarbon in the sample
relative to the carbon number of normal paraffins. The gas chromato-
graphs and boiling point profiles for the "A", "B", and "C" plots are
shown in Figures 28, 29, and 30, respectively. Crude oil tank bottoms
(Figure 28) contains components whose carbon numbers, relative to
normal paraffins, range from about 5 to 40. The normal paraffin con-
tent was substantial, based upon a peak for each normal paraffin carbon
number. The initial boiling point was less than 50°C, and about 80
percent weight of the sample boiled at a temperature less than 400°C
or equivalent to about 25 carbon numbers (based upon n-paraffins).
For the highest temperature reached, 511°C (equivalent to 38 n-paraffin
carbon numbers), about 95 percent weight of the sample had passed
through the gas chromatograph column. (Residuals were back-flushed
from the column to obtain a material balance.)
\
Residual oil at the start of the project contained carbon numbers
ranging from about 20 to >38 relative to normal paraffins. The boiling
point profile ranged from about 350 to 510°C at about 70 percent weight
of the sample passing through the column. Detector response peaks did
not coincide with normal paraffin carbon numbers.
Residual oil extracted from soil plots A-l and A-3 at the end of the
project period (Figure 28) appears quite different from the oil added
and the starting residual oil. The carbon number range was about 15
to >38 for each of the three oils. The initial boiling point was
53
-------
FIGURE 28
CRUDE OIL TANK BOTTOMS
OIL ADDED
20
10
_
Di.
00
O
CL.
00
CsL
O
LU
O
RESIDUAL'OIL"AT START
20
10
RESIDUAL OIL AT END
20
10
A-2
20
10
A-3
400
200
200
o
o
A-l ^
" I Q;
400
200
400
200
400
200
10 20 30
CARBON NUMBER-OF N-PARAFFIN PEAK
20 40 60, 80
PERCENT WEIGHT'
GAS CHROMATOGRAPH AND BOILING POINT PROFILES, "A" PLOTS
54
-------
FIGURE 29
20
10
OIL ADDED
BUNKER C FUEL OIL
20
10
UJ
o:
UJ
Q-
UJ
00
o
o.
00
O
UJ
a
RESIDUAL OIL AT START
20
10
RESIDUAL OIL AT END
20
10
20
10
B-l
B-2
B-3
200
200
200
10 20 30
CARBON NUMBER OF N-PARAFFIN PEAK
20 40 60
PERCENT WEIGHT
GAS CHROMATOGRAPH AND BOILING POINT PROFILES, "B" PLOTS
55
-------
20
10
OIL ADDED
20
10
o
DC
o
a.-
a:
o
RESIDUAL OIL AT START
20
10
RESIDUAL OIL AT END
20
10
FIGURE 30
WAXY
RAFFINATE
-------
about 200°C and the percent weight up to 510°C was about 45 and 65 for
plots A-l and A-3, respectively. Normal paraffin peaks were not
apparent for plot A-l. The detector response for oil extracted from
the A-3 plot showed small peaks at carbon numbers 16, 22, 23, 25, and
28, indicating incomplete microbial reaction. Also, the residual oil
at the end of the project was different from the residual oil at the
start, indicating the starting residual oil had been changed during
the project. Therefore, the starting residual oil was not a stable,
nonreactive material.
Chromatographs and boiling point profiles for the "B" plots (Figure 29)
are similar to the "A" plots discussed above. Differences appear in
the percent weight boiling less than 510 C due to the higher boiling
bunker C fuel oil which was added to the "B" plots. Also as expected,
normal paraffin peaks for bunker C fuel oil were not apparent. Again
the residual oils at the start and end of the project were different.
Results for the "C" plots which received waxy raffinate (Figure 30)
show predominant normal paraffin peaks in the oil added to the soil
and some definite peaks in the residual oil at the end of the project.
This was expected since the hydrocarbon type analyses (Figure 24)
showed unreacted saturates present for all plots (C-l and C-3). The
residual oil at the start and end (Figure 30) of the project appear
different, indicating a reaction of the starting residual oil has
occurred especially in the carbon number range of 30 to 35.
57
-------
SECTION XIV
RAINFALL RUNOFF
Rainfall accumulated and was trapped in the plot area as discussed
previously. Drainage of the plots was controlled, and a sample of the
runoff water was obtained for analysis. On a few occasions during ex-
cess rainfall periods, water overflowed the plots. Analyses of the
water for oil, ammonia, nitrate, and phosphate contents indicated that
little, if any, of these constituents were present when drained imme-
diately after a rain. Long standing appeared to cause higher oil
contents. The oil content ranged from about 30 to 100 mg/1, and the
oil content of water from the fertilized plots as discussed earlier
were found to contain the highest concentration of organic acids.
Each plot was drained about 36 times during the 18-month project, and
many times the plots were only partially full but needed to be dry for
cultivation. Based upon an average oil content of 60 mg/1, about 0.6
pounds of oil was discharged during the 17-month experimental period.
This quantity equals about 0.03 lbs/ft3 of oil in the soil, and adjust-
ments in earlier decomposition rate determinations for such a small
quantity were not considered justifiable.
Infrared examination of oil recovered from rainfall runoff water is
discussed in Appendix D and indicated the oil to be organic acids with
characteristics quite similar with spectra for naphthenic acids.
Ammonia content of the water appeared to vary with the soil nutrient
content. During periods when the ammonia was excessive on the No. 1
plots, discharge water contained up to 150 mg/1 ammonia as N. Nitrates
and phosphates were generally absent in the discharges.
59
-------
SECTION XV
ACKNOWLEDGMENTS
Facilities, personnel, and partial (30%) financial support were
furnished by Shell Oil Company. A financial grant (70%) and
guidance were supplied by the Environmental Protection Agency.
Dr. Melvin L. Renquist, now retired, and Dr. Ben S. Baldwin, Chief
Technologist, served as Grant Directors and provided the necessary
administrative assistance for the project.
Mr. C. Buford Kincannon, Senior Engineer, directed the project
activities and prepared the initial and final reports.
Mr. Wilbert L. Pegues, Laboratory Technician, performed laboratory
tests, supervised the experimental tasks of the plot area, and col-
lected data.
Mr. James M. Martin, Senior Research Chemist, provided infrared
spectra data and interpretation of the infrared results.
Consultants during the project were Dr. Edwin 0. Bennett, Micro-
biologist, University of Houston, and Dr. Warren D. Anderson,
Soil Specialist, Texas A&M University.
From the Environmental Protection Agency, valuable guidance was
provided by Mr. Leon H. Myers, Project Officer, and the final
report was reviewed by Dr. Thomas E. Short, Chemical Engineer.
61
-------
SECTION XVI
REFERENCES
1. G. K. Dotson, R. B. Dean, B. A. Kenner, and W. B. Cooke, Land
Spreading, A Conserving and Non-Polluting Method of Disposing of
Oily Wastes, Proceedings of the Fifth International Water Pollu-
tion Research Conference, Vol. 1, Section II, 36/1-36/15,
Pergamon Press, 1971.
2. K. J. Stracke, Cleanup at Santa Barbara, Paper No. SPE3197, 1970,
Society of Petroleum Engineers of AIME.
3. J. B. Davis, Petroleum Microbiology, Elsevier Publishing Company,
New York, N.Y., 1967.
4. Manual on Disposal of Refinery Wastes, Volume on Liquid Waste,
Chapter 13, Biological Treatment, First Edition 1969, American
Petroleum Institute, Division of Refining, New York, N.Y.
5. Standard Methods for the Examination of Water and Wastewater,
Twelfth Edition, American Public Health Association, Washington,
B.C.
6. Robert S. Breed, E. G. D. Murray, and Nathan R. Smith, Bergey's
Manual of Determinative Bacteriology, Seventh Edition, The
Williams and Wilkins Company, Baltimore, Maryland.
7. L. E. Philyaw, A. E. Krc, and M. J. O'Neal (Shell Oil Company),
Anal. Chem., 43, #6, 787-89, May 1971.
8. American Society for Testing and Materials, ASTM, Standard Method
of Test for Sediment in Crude and Fuel Oils by Extraction, ASTM
D473-65.
9. American Society for Testing and Materials, ASTM, Standard Method
of Test for Characteristic Groups in Rubber Extender and Process-
ing Oils by the Clay-Gel Adsorption Chromatographic Method, ASTM
D2007-69. ,
10. State Soil Testing Laboratories in the Southern Region of the
United States, Bulletin No. 102, Southern Cooperative Series,
June 1965, Agricultural Experimental Station Publication.
11. Improved Kjeldal Method for Nitrate Containing Samples, Official
Methods of the Association of Official Agricultural Chemist, 1965,
Pg. 16.
12. American Society for Testing and Materials, ASTM, Standard Method
of Test for Sulfur in Petroleum Products, High Temperature Method,
ASTM D1552-64.
63
-------
13. M. Gales, Jr., E. Julian, and R. Kroner, Method for Quantitative
Determination of Total Phosphorus in Water, Journal AWWA, 58,
No. 10, 1363 (1966).
14. American Petroleum Institute, API, Manual on Disposal of Refinery
Wastes, Volume IV, Sampling and Analysis of Waste Water, Second
Edition, 1957, Volatile and Non-Volatile Oily Material, API,
Method 731-53.
15. V. Carlson, E. 0. Bennett, and J. A. Rowe, Microbial Flora and
Their Relationship to Water Quality, Society of Petroleum
Engineering Journal, Volume 1, Pg. 71-80, 1961.
-------
SECTION XVII
APPENDICES
A. Analytical Results
Table 1:
Table 2:
Table 3:
Table 4:
Table 5:
Table 6:
Table 7:
Table 8:
Table 9:
Table 10:
Table 11:
Table 12:
Table 13:
Table 14:
Oil Properties for Simulated Sludges A, B, and C
Oil Content of Individual Soil Samples for
"A" Plots
Oil Content of Individual Soil Samples for
"B" Plots
Oil Content of Individual Soil Samples for
"C" Plots
Chronological Data for "A" Plots
Chronological Data for "B" Plots
Chronological Data for "C" Plots
Total Nitrogen, Sulfur, Phosphorus, and
Metals Contents for "A" Plots
Total Nitrogen, Sulfur, Phosphorus, and
Metals Contents for "B" Plots
Total Nitrogen, Sulfur, Phosphorus, and
Metals Contents for "C" Plots
Oil and Nutrient Penetration Depths Into Soil
Hydrocarbon Types for "A" Plots
Hydrocarbon Types for "B" Plots
Hydrocarbon Types for "C" Plots
B. Microbial Analyses
Table 1: Predominant Individual Organisms for
Table 2: Predominant Individual Organisms for
Table 3: Predominant Individual Organisms for
Brief Description of Predominant Organisms
C. Microbiology Consultant's Comments
Table 1: Statistics of Microbial Analysis
Microbiology Consultant Report
D. Infrared Study of Oils Extracted from Soil
Infrared Study of Rainfall Runoff Water
Oil Content in Soil Samples
Sketch: Apparatus for Extraction of Oil in Soil
Page
No.
66
67
68
71
74
77
80
83
86
88
90
92
93
94
95
96
"A" Plots
"B" Plots
"C" Plots
97
99
101
103
106
107
108
109
113
114
115
-------
APPENDIX A
ANALYTICAL RESULTS
The three simultaneous experiments using crude oil tank bottoms on the
"A" soil test plots, bunker C (No. 6) fuel oil on the "B" plots, and
waxy raffinate on the "C" plots, were.similar. Properties of the oils
added to the soils are given in Table 1. Oil contents of subsamples
from each soil plot described in Section IX are given in Tables 2, 3,
and 4 for the "A", "B", and "C" plots, respectively. Subsample results
from each plot were averaged, and the averaged values are also given in
Tables 5, 6, and 7. These tables alsorinclude soil moisture, pH, oil,
soluble nitrogen (ammonia, NHg and nitrate, NO3), soluble phosphorus
(phosphate, PO^, expressed as P20s) and total aerobic microorganism
content and temperature, all listed chronologically. The number of
plowings between sampling dates and the oil and fertilizer addition
dates have been included with the chronologically recorded data
(Tables 5, 6, and 7).
Metals, nitrogen, phosphorus, and sulfur contents of the soil are given
in Tables 8, 9, and 10 for test plots "A", "B", and "C", respectively.
Oil and nutrient contents of soil taken at depths of 2, 4, and 6 feet
are given in Table 11.
Oil extracted from the soil test plots and oil added to the soil were
analyzed for hydrocarbon types, infrared and gas chromatography charac-
teristics. Hydrocarbon types for the "A", "B", and "C" plots are given
in tables 12, 13, and 14, respectively. The infrared and gas chrbmato-
graphic data are presented graphically and discussed in Section XIII.
(Details of the infrared study are given in Appendix D.)
66
-------
APPENDIX A
TABLE 1
OIL PROPERTIES
SIMULATED SLUDGES A, B, AND C
SPEC. GRAV., 60/60°F
LBS/GAL
POUR POINT, °F
VISCOSITY, SU, 60°F
SSF, 122°F
HYDROCARBON TYPE, %w
SATURATE
RESINS
AROMATIC
TOTAL SULFUR, %w
TOTAL NITROGEN, %w
TOTAL PHOSPHORUS, PPM
TOTAL ASH, PPM
CALCIUM
MAGNESIUM
SODIUM
IRON
COPPER
LEAD
TANK
BOTTOMS
31,000
1,880
375
3,135
1,255
94
Nil
A
CRUDE OIL
0.86
7.12
-5
60
36
8
56
0.47
0.09
6
SLUDGE
B
BUNKER C
1.03
8.57
40
19,000
120
18
26
56
1.96
0.41
11
320
10
1
15
20
1
Nil
C
WAXY PRODUCT
0.85
7.08
95
-
59
90
-
10
0.04
O.0005
5
8
Nil
Nil
Nil
Nil
Nil
—
67
-------
APPENDIX A
TABLE 2
OIL CONTENT OF INDIVIDUAL SOIL SAMPLES
PERCENT WEIGHT
Plot
Sub -Sample
Date
4-22-70
5-13
5-19
5-27
6-11
6-24
7-10
7-29
8-14
8-27
9-10
9-22
10-16
A-l
a
8.9
8.3
13.1
11.5
13.3
14.0
14.4
13.8
13.1
11.4
11.1
11.9
11.3
b
10.8
10.2
12.1
14.7
16.1
15.7
14.9
15.6
17.7
15.1
15.0
14.2
11.1
11.8
11.3
c avg.
9.6 10
9.4 10
12.5 13
15.4 14
14.3 14
15.4 15
15.3 16
14.2 14
13.9 14
13.9 13
11.0 11
12
11.4 11
a
11.5
12.7
15.0
15.8
16.4
15.5
17.4
15.7
14.3
14,2
13.6
13.6
13.4
FOR "A" PLOTS
A-2
b
10.6
12.4
13.6
16.8
17.6
18.1
16.9
17.7
16.7
15.6
16.2
15.5
13.9
13.4
13.7
c avg.
10.6 11
14.2 13
17.2 16
14.9 16
17.3 17
17.6 17
16.7 17
15.4 16
16.1 16
15.7 15
13.6 14
14
13.4 14
a
11.1
13.6
14.1
15.4
15.3
15.5
—
18.2
17.0
16.3
17.2
17.9
17.4
15.9
16.3
A-3
b
10.6
13.7
15.2
14.9
16.0
17.5
17.5
17.2
17.9
17.3
17.3
17.2
17.2
18.0
18.1
16.0
16.0
c avg.
11.0 11
12.1 13
14.4 15
16.0 16
17.2 17
15.8 17
18.8 18
17.8 17
17.1 17
16.7 17
17.9 18
16
15.5 16
16.3
-------
APPENDIX A
TABLE 2 (CONTD.)
VO
Plot
Sub-Sample
Date
10-30-70
11-13
12-7
1-6-71
1-27
2-12
2-24
3-10
3-24
4-7
4-21
5-5
5-19
A-l
a
10.1
11.4
11.7
11.2
10.2
18.7
21.9
17.1
17.9
17.1
17.2
16.6
15.8
b
11.3
12.0
11.5
11.2
11.0
20.5
23.5
17.4
19.6
18.8
18.2
17.1
16.0
c
10.3
11.0
10.8
10.8
9.9
30.3
20.9
19.3
17.8
16.9
18.1
16.1
16.1
avg.
11
12
11
11
10
23
22
18
18
18
18
17
16
a
12.7
12.8
12.7
12.5
11.4
23.3
25.2
24.3
22.7
21.9
23.1
20.5
21.6
A-2
b
12.9
13.8
13.7
13.6
13.4
26.8
25.4
22.8
26.3
23.8
24.1
21.4
22.4
c
13.6
14.2
13.8
14.0
12.8
28.6
24.8
27.9
23.9
20.7
22.7
21.1
20.8
avg.
13
14
13
13
13
26
25
25
24
22
23
21
22
a
15.4
15.4
15.1
14.9
14.8
23.4
27.3
33.1
30.1
29.0
25.3
22.6
25.3
A-
b
16.4
16.2
16.7
16.1
16.3
16.0
15.3
15.6
15.6
15.8
26.1
26.1
31.1
32.0
35.2
30.2
36.0
35.7
24.8
24.8
24.4
23.8
23.8
23.1
25.1
26.3
-3
c
15.4
15.7
15.2
15.2
15.1
26.3
26.1
25.6
25.0
21.5
21.9
22.4
21.5
avg
16
16
16
15
15
25
28
30
30
25
24
23
24
-------
APPENDIX A
TABLE 2 (CONTD.)
Plot
Sub-Sample
Date
6-2-71
6-30
7-14
7-28
8-11
8-25
9-23
9-29
A-l
A-2
a
15.4
15.4
13.3
14.4
14.4
13.0
13.1
12.5
b
14.8
15.9
15.1
14.4
14.3
12.1
13.7
12.4
c
15.7
16.5
13.9
14.2
13.5
13.0
14.1
12.2
&VR.
15
15
14
14
14
13
14
12
A-3
18.0 20.6 21.5 20
18.3 19.2 17.9 19
18.1 18.4 18.1 18
19.4 18.7 16.7 18
18.1 17.9 16.5 18
16.7 16.2 15.7 16
15.4 16.2 16.7 16
16.3 15.9 15.8 16
22.8- 24.3 23.9 24
23.6
21.8 22.0 23.4 23
21.7
23.9 21.5 19.6 22
23.4
21.3 22.7
21.8 19.2 21
22.4 20.7 20.1 21
20.4
20.7 19.3 17.9 19
19.9
20.6 20.2 19.9 20
19.8
22.6 21.2 19.0 21
-------
Plot
Sample Point
Date
4-22-70
5-13
5-19
5-27
6-11
6-24
7-10
7-29
8-14
8-27
9-10
9-22
10-16
APPENDIX A
TABLE 3
OIL CONTENT OF INDIVIDUAL SOIL SAMPLES FOR "B"
PERCENT WEIGHT
B-l B-2
a
10.3
10.2
30.6
25.6
24.8
26.0
25.0
23.9
24.0
22.0
19.7
18.9
17.5
b
10.8
10.6
14.0
29.9
27.2
27.2
24.2
24.4
25.8
24.4
21.9
20.7
19.6
18.9
16.6
11.0
13.2
32.7
24.6
23.8
24.9
24.5
23.4
22.3
21.5
19.5
—
17.9
ave.
11
13
31
26
24
25
25
24
23
21
20
19
17
a
9.4
10.8
29.6
22.2
24.7
23.0
25.4
19.8
19.6
18.7
16.4
16.6
15.8
b
9.5
10.2
10.3
29.4
23.8
18.7
25.0
20.0
19.5
18.8
19.4
18.2
16.8
16.6
15.5
c
11.9
10.9
29.5
23.6
20.3
22.8
20.5
20.3
18.5
19.1
17.1
~
15.4
PLOTS
avg.
10
11
30
23
21
24
22
20
19
19
17
17
16
B-3
a
10.0
12.2
25.6
22.0
24.6
24.1
23.6
23.5
22.1
18.7
19.4
18.8
19.0
19.1
b
9.5
11.8
27.9
27.1
23.4
20.7
24.1
25.3
21.6
19.6
19.7
17.6
17.7
18.8
18.8
19.0
18.5
17.5
c
10.8
13.1
26.6
22.0
18.0
23.4
21.2
19.0
18.9
19.2
18.6
--
18.8
avg.
10
12
28
22
21
24
23
21
19
19
19
19
19
-------
APPENDIX A
TABLE 3 (CONTD.)
N5
Plot
Sample Point
Date
10-30-70
11-13
12-7
1-6-71
1-27
2-12
2-24
3-10
3-24
4-7
4-21
5-5
5-19
B-l
a
17.3
17.7
15.5
16.2
15.9
35.2
38.0
38.1
48.7
34.2
32.2
31.5
32.5
b
17.4
17.1
15.7
16.2
14.7
33.7
36.4
45.5
41.5
33.3
33.6
31.5
34.4
c
17.3
17.0
17.7
16.3
15.2
29.3
40.0
47.8
43.0
34.6
32.3
36.0
35.3
17
17
16
16
15
33
38
44
44
34
33
33
34
a
14.9
15.7
16.0
14.7
14.3
30.6
34.7
36.5
41.5
33.3
32.6
32.5
34.6
B-2
b
14.6
15.5
15.9
15.0
13.2
38.2
35.5
42.2
38.5
35.0
32.4
33.1
35.4
c
15.3
15.6
15.1
15.4
13.3
30.6
43.4
40.2
37.7
36.4
31.4
32.8
37.7
15
16
16
15
14
33
38
40
39
35
32
33
36
a
16.9
17.8
17.9
17.6
17.2
33.1
33.9
32.9
36.6
31.8
29.0
26.7
37.5
B-
b
17.4
17.3
16.9
17.1
18.4
18.5
17.2
17.4
15.4
15.4
31.9
33.1
34.0
32.3
35.6
33.4
35.5
34.8
34.8
33.9
31.7
30.4
30.7
29.7
35.2
36.6
3
c
16.8
17.0
17.6
17.8
16.5
34.9
34.7
34.0
36.4
36.0
28.5
36.0
34.9
17
17
18
18
16
33
34
34
36
34
30
31
36
-------
APPENDIX A
TABLE 3 (CONTO.)
Plot
Sample Point
Pate
6-2-71
6-30
7-14
7-28
8-11
8-25
9-23
9-29
B-l
B-2
37.6 37.3 31.3 35
33.2 31.9 30.0 32
34.8 32.2 31.0 33
36.2 34.2 26.9 32
28.9 31.7 32.4 31
29.6 29.2 28.9 29
29.1 25.9 22.6 26
24.2 25.4 25.7 25
a
36.3
36.4
35.7
38.6
26.6
30.0
b
36.2
38.8
37.6
36.5
25.7
20.8
c
38.7
34.0
39.1
31.8
29.5
21.6
avg.
37
36
38
36
27
24
B-3
30.6 19.9 22.2 24
25.4 24.1 22.0 24
35.6 29.8 28.5 31
33,0 31.2 33.3 33
36.1
33.5 36.1 28.5 33
35.3
31.1 30.4 32.2 31
31.1
34.8 30.4 29.6 32
30.9
34.3 29.7 31.9 32
26.8
26.4 25.5 26.7 26
26.2
31.2 26.8 32.0 30
28.1
-------
Plot
Sample Point
Date
4-22-70
5-13
5-19
APPENDIX A
TABLE 4
OIL CONTENT OF INDIVIDUAL SOIL SAMPLES FOR "C" PLOTS
PERCENT WEIGHT
C-l C-2 C-3
a b c avg. a b c avg. a b c avg.
9.4 10.5 10.6 10 9.4 9.6 9.6 10 10.6 9.9 10.3 10
10.7
10.6 11.9 13.2 11 9.5 12.2 13.8 12 9.0 12.1 12.6 11
12.4
23.4 23.0 24.2 24 16.7 20.8 22.6 20 17.3 18.1 20.5 19
5-27
6-11
6-24
7-10
7-29
8-14
8-27
9-10
9-22
20.3 23.0 23.1 22
22.8
21.6 21.7 22.7 22
19.2 20.4 16.4 19
19.3
17.3 17.2 25.6 20
16.9 19.1 21.5 19
17.4 18.5 19.1 18
14.8 17.4 18.4 17
15.8 15.5 15.8 16
18.5 22.9 24.6 22
16.2 20.5 22.6 20
12.8 16.0 18.3 16
15.8
24.3 18.1 22.4 22
16.7 18.2 20.1 18
16.7
16.9 15.7 19.3 17
12.8 13.5 18.2 15
14.2 14.3 12.8 14
18.3
18.3 19.1 19.5 19
17.4 19.8 20.5 19
17.2
15.5 18.7 17.4 17
18.6
15.4 18.8 17.8 17
15.5
15.6 17.9 19.2 18
15.4
14.2
14.4
17.1
17.2
16.7
16.8
14.4
14.3
14.2 14.2
14
12.8 12.9
13
15.3 15.2
17.8 17
16.1 16
15.4 15
15
-------
APPENDIX A
TABLE 4 (CONTD.)
Ln
Plot
Sample Point
Date
10-16-70
10-30
11-13
12-7
1-6-71
1-27
2-12
2-24
3-10
3-24
4-7
4-21
5-5
C-l
a
12.8
11.5
12.1
11.2
11.8
11.2
27.8
29.8
27.7
23.9
22.1
21.1
21.7
b
14.6
11.7
13.8
14.1
13.2
12.5
30.9
32.6
25.9
26.7
27. 4
25.9
26.7
c
15.1
13.1
13.8
14.7
13.7
12.1
32.9
37.3
32.2
28.9
25.9
24.6
23.6
14
12
13
13
13
12
31
33
29
27
25
24
24
a
10.9
13.2
10.9
io.s
10.8
10.4
29.5
29.8
31.0
24.7
24.7
26.2
24.6
C-2
b
13.1
12.2
13.5
11.8
12.6
12.4
26.5
29.5
29.9
27.9
26.4
24.6
26.6
c
15.3
14.8
11.7
13.4
13.0
13.7
30.9
33.2
29.8
28.9
27.0
25.4
25.9
13
13
12
12
12
12
29
31
30
27
26
25
26
a
13.8
12.7
13.0
12.8
12.5
12.9
24.0
25.9
26.7
26.4
25.4
24.5
24.9
C-
b
16.3
16.8
14.5
14.9
14.0
14.5
14.4
14.7
14.3
14.7
14.1
14.0
26.3
26.7
28.9
27.9
28.6
27.2
27.5
27.8
26.5
26.6
25.6
25.8
25.7
25.8
•3
c
16.4
14.0
13.2
14.2
14.6
14.5
31.3
30.1
30.5
29.9
28.9
28.9
27.9
16
14
13
14
14
14
27
28
29
28
27
26
26
-------
APPENDIX
TABLE 4 (CONTD.)
Plot
Sample Point
Date
5-19-71
6-2
6-30
7-14
7-28
8-11
8-25
9-23
9-29
C-l
C-2
C-3
21.1 23.4 24.6 23
19.9 23.7 23.4 22
19.2 22.0 23.3 22
18.3 21.7 22.1 21
17.4 21.1 21.5 20
20.4 23.4 17.9 21
17.6 20.7 18.4 19
16.9 18.2 21.2 19
14.4 18.4 19.6 18
23.9 26.1 25.0 25
24.5 25.4 25.9 25
22.5 23.9 23.5 23
21.5 24.1 24.1 23
21.5 24.2 22.0 23
22.4 25.3 28.2 25
20.6 21.7 21.5 21
22.2 24.5 24.8 24
17.9 15.8 18.5 18
29.4 27.7 30.2 29
28.6
25.0 26.0 28.9 27
22.0 26.3 27.8 25
27.2
24.3 27.7 28.4 26
26.3
27.1 27.4 23.9 26
28.1
27.1 24.6 28.7 27
25
21.9 22.0 22.4 22
22.9
21.8 26.0 26.6 25
24.8
20.8 23.1 24.2 23
23.2
-------
APPENDIX A
TABLE 5
CHRONOLOGICAL DATA
CRUDE OIL TANK BOTTOMS, "A" PLOTS
1970
pH, Before Extr.
pH, After Extr.
Moisture, 7.w
Oil, %w
NHo as N, ppm
NO 3 as N, ppm
PO as P 0 , ppm
25'
Temperature, °F
Ambient
Total Count
Aerobes x 107
x 10'
x 107
Number Plowings
Between Sample
Da tea
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
APR.
22
6.6
6.9
6.8
11
11
12
10
11
11
Nil
Nil
Nil
Nil
Nil
Nil
100
78
80
MAY
7 13 17
7.3
7.0
7.2
6
6
8 6
o
•g. 10
o 13
•g. 13
1 72°
« 22°
Z Nil %
3 0
TJ N-H *S
flj 1H 1 1 ^
5 Nil 3
< Nil <
77 80
81
3
0.4
2
1
JUNE JULY
19 27 11
6.8
6.8
6.8
17 20 12
20 20 8
19 20 8
13 14 14
16 16 17
15 16 17
30
25
Nil
Nil
Nil
Nil
83 83
80 82 82
170
190
10
2 1 1
24 10
7.0
7.0
7.0
8 18
10 20
10 17
15 16
17 17
17 18
30
20
Nil
3
1
Nil
240
165
95
86
76
38
73
87
1 1
29
7.3
9
6
6
14
16
17
3
Nil
Nil
Nil
Nil
Nil
89
87
1
AUGUST
7 14
6.8
6.8
6.8
7
7
z 7
o
•g. 14
3 16
•a i?
1 1525
. 750
Z Nil
3
•g Nil
3 Nil
< Nil
320
200
89 94
86 86
54
62
6
2
27
6
7
7
13
15
17
94
83
1
77
-------
APPENDIX A
TABLE 5 (CONTD.)
CHRONOLOGICAL DATA
CRUDE OIL TANK BOTTOMS, "A" PLOTS
SEPT.
pH, Before Extr.
pH, After Extr.
Moisture, %w
Oil, %w
NH, as N, ppm
J
NO as N, ppm
j
PO, as P 0 , ppm
H ft J
Temperature, °F
Ambient
Total
Aerobes x 10.
x 10,
x 10'
Number Plowings
'Between Sample
Dates
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
10
7.0
7.0
7.0
6
5
5
11
14
18
565
30
Nil
Nil
Nil
Nil
92
82
5
22
6.7
6.7
6.8
5
4
4
12
14
16
500
20
Nil
Nil
Nil
Nil
88
83
48
40
7
0
1970
OCT.
16 31
6.6
6.8
6.9
6 6
8 5
4 5
11 11
14 13
16 16
540
140
Nil
Nil
Nil
Nil
720
370
68 62
62 65
84
104
4
3 3
NOV.
14
6.7
6.9
7.0
15
11
6
12
14
16
Nil
Nil
Nil
Nil
Nil
Nil
630
165
85
63
60
119
32
26
3
DEC.
17
6.2
6.5
6.8
12
9
6
11
13
16
50
40
Nil
Nil
Nil
Nil
680
290
58
61
94
56
7
5
JAN.
6
6.3
6.7
6.7
15
11
4
11
13
15
50
10
Nil
Nil
Nil
Nil
500
290
90
43
38
71
37
122
2
27 2
6.5
6.7
6.8 ^
•H
0
7 T,
5 >g
5 «j.
10
13
15
en
O
sr to
• 3! «_
z o
9)
•O TJ
3 S
570
220
150
64 57
64 58
62 55
60 43
3
1971
FEB.
12 24
6.7
6.9
6.7
23 10
22 15
23 20
23 22
26 25
25 28
390
260
Nil
25
Nil
Nil
540
200
130
61 92
59 62
59 60
58 65
53
11
37
4 2
MARCH
10
6.6
6.7
6.9
20
17
20
18
25
31
255
150
Nil
Nil
Nil
Nil
73
66
66
70
77
52
6
1
24
10
9
12
18
24
30
80
73
70
58
2
78
-------
APPENDIX A
TABLl- 5 (CONTD.)
CHRONOLOGICAL DATA
CRUDE OIL TANK BOTTOMS, "A" PLOTS
1971
APRIL
pH, Before Extr.
pH, After Extr.
Moisture, %w
Oil, 7.w
NH3 aa N, ppm
NO 3 as N, ppm
PO^ as P2°5' PP™
Temperature, °F
Ambient
Total 7
Aerobes x 10_
x 10,
x 10'
Number Plowings
Between Sample
Dates
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
7
6.2
6.3
6.7
6
6
8
17
22
25
120
85
Nil
0
0
0
470
210
95
84
88
80
67
16
10
0.5
2
21
11
7
7
18
23
24
<*i
*5f
•o
01
•o
3
86
89
86
75
2
MAY
5
6.7
6.8
6.9
b
6
6
17
21
23
140
60
Nil
30
10
0
470
160
95
86
87
82
80
2
19
7
5
7
16
22
24
90
98
94
82
100
30
1
1
JUNE
2 30
6.6
6.7
7.0
5 16
4 13
6 15
15 15
20 19
24 23
165
80
Nil
25
10
0
500
210
95
90 92
90 94
87 90
83
97
6b
8
1 3
JULY AUGUST
14
6.7
6.8
7.0
10
4
6
14
18
22
50
25
Nil
5
Nil
Nil
580
210
95
96
94
92
84
48
14
21
2
28 11
6.4
6.5
6.7
6.7
6.8
6.9
12 21
5 18
6 15
14 14
18 18
21 21
PI
%
£
•a
01
•o
•o
580
210
95
95 88
93 92
91 88
86 83
58
59
35
1 1
25
7.0
7.1
7.3
5
4
4
13
16
20
175
70
Nil
65
40
Nil
580
210
125
99
96
91
84
10
SEPT.
25
6.8
7.0
7.3
6.9
7.1
7.2
16
14
12
14
16
20
120
20
Nil
20
Nil
Nil
410
200
115
80
82
82
78
30
12
16
21
79
-------
APPENDIX A
TABLE 6
CHRONOLOGICAL DATA
BUNKER C (NO. 6) FUEL OIL, "B" PLOTS
pH, Before Extr.
pH, After Extr.
Moisture, 7.w
Oil, 7.w
NH3 as N, ppm
NOj as N, ppm
P04 as P205, ppm
Temperature, °F
Ambient
Total ?
Aerobes x 10
x 10;
x 10'
Number Blowings
Between Sample
Dates
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
APR.
22
6.9
7.0
7.0
12
13
11
11
10
10
Nil
Nil
Nil
Nil
Nil
Nil
94
78
80
1970
MAY JUNE JULY
7
m
3
p
o
•s.
0)
O
•i.
*o
c
(0
a
«>
ij
3
•a
a)
•o
•o
77
1
1
0.6
13
7.3
7.3
7.3
7
7
6
13
11
12
980
700
Nil
Nil
Nil
Nil
80
81
1
17 19 27 11
6.9
6.9
7.0
677
775
896
31 26 24
30 23 21
28 22 21
220
60
3 Nil
0
U Nil
5 Nil
< Nil
83 83
78 82 82
10
12
5
211
24 10
7.1
7.1
7.2
5 14
6 12
6 13
25 25
24 22
24 23
140
15
Nil
Nil
Nil
Nil
180
150
105
86
76
41
27
11
1 1
29
7.5
4
4
6
24
20
21
10
Nil
Nil
Nil
Nil
Nil
89
87
1
7
CO
3
h
o
•g.
CO
o
i.
•o
§
a]
0)
M
3
•0
4)
•O
"O
<
89
86
AUGUST
14
6.9
6.9
6.9
4
4
5
23
19
19
1100
675
Nil
Nil
Nil
Nil
770
260
94
86
5
6
1
2
27
4
4
5
21
19
19
94
83
1
80
-------
APPENDIX A
TABLE 6 (CONTD.)
CHRONOLOGICAL DATA
BUNKER C (NO. 6) FUEL OIL, "B" PLOTS
1970
1971
SEPT.
pH, Before Extr.
pH, After Extr.
Moisture, %w
Oil, Xw
NH, as N, ppm
J
NO. as N, ppm
PO as P 0 , ppm
H £. J
Temperature, 8F
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
10
7.0
7.1
7.0
5
5
6
20
17
19
655
55
Nil
Nil
Nil
Nil
92
22
6.6
6.8
6.9
5
5
4
19
17
19
420
35
Nil
Nil
Nil
Nil
88
OCT. NOV.
16
6.5
6.7
6.9
6
7
6
17
16
19
220
195
Nil
Nil
Nil
Nil
800
360
68
31 14
6.7
6.9
7.1
5 15
6 14
4 8
17 17
15 16
17 17
Nil
Nil
Nil
Nil
Nil
Nil
920
62 63
DEC.
17
5.8
6.3
6.6
12
8
5
16
16
18
30
20
Nil
Nil
Nil
Nil
1100
285
175
58
JAN.
6
6.1
6.5
6.7
6
8
8
16
15
17
20
10
Nil
Nil
Nil
Nil
900
275
130
43
27 2
6.3
6.5
6.9 3
o
8 1
6 5
4 <
15
14
16
n
O
Z Si
•& to
a: a
z u
0
~O CU
HI
•u -o
•o c
< a
1125
270
140
68 58
64 56
59 54
FEB.
12 24
6.4
6.8
7.0
8 8
9 8
8 7
33 33
33 33
33 33
524
412
Nil
110
120
Nil
1160
300
140
59 60
59 62
59 62
MARCH
10
6.5
6.8
6.9
9
9
9
33
33
33
634
254
Nil
50
35
Nil
825
210
110
68
70
74
24
8
8
9
33
33
33
69
68
68
Ambient
Total
82
83
62
65
60
61
38
60 43
58 65
70
58
Aerobes x 10' B-l 37 155 80 73 210 3
x 10' B-2 28 27 75 18 21 2
x 10' B-3 3 3| 27 3 53 3 3
Number Plowirigs
Between Sample
Dates
50333523 42 12
81
-------
APPENDIX A
TABLE 6 (CONTD.)
CHRONOLOGICAL DATA
BUNKER C (NO. 6) FUEL OIL, "B" PLOTS
APRIL
pH, Before Extr.
pH, After Extr.
Moisture, %w
Oil, %w
NHo as N, ppm
NOj as N, ppm
P04 as P205> ppm
Temperature, °F
Ambient
Total
Aerobes x 10
xlO7,
x 10'
Number Flowings
Between Sample
Dates
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
7
6.6
6.8
6.9
9
7
9
34
35
34
630
370
Nil
20
Nil
Nil
930
240
100
90
96
93
67
5
0.1
0.1
2
21
6
8
9
33
32
30
CO
%
g
•o
0)
•o
•0
94
92
87
75
2
MAY
5
6.9
6.9
7.0
6
6
7
33
33
31
440
300
Nil
100
5
Nil
750
220
100
85
84
83
80
2
19
3
3
3
34
36
36
102
103
101
82
4
10
30
1
JUNE
2 30
6.9
7.0
7.1
3 5
3 5
3 4
35 32
37 36
31 33
410
290
Nil
20
1
Nil
840
230
80
92 96
92 94
92 92
83
3
2
3
1 3
1971
JULY AUGUST
14
6.9
7.0
7.1
3
2
2
33
38
33
360
170
Nil
15
1
Nil
900
230
95
93
95
93
84
5
4
1
2
28 11
6.3
6.5
6.7
6.5
6.6
6.7
3 6
3 6
3 6
32 31
36 27
31 32
fl
8,
^
0)
•a
•a
800
230
95
94 90
93 90
93 88
86 83
54
30
0.5
1 1
25
7.1
7.2
7.3
2
2
2
29
24
32
430
230
Nil
145
125
Nil
740
250
130
95
95
94
84
10
SEPT.
25
6.8
7.0
7.2
6.9
7.0
7.2
4
6
4
26
24
26
116
Nil
Nil
Nil
Nil
Nil
680
230
115
82
81
81
78
30
25
22
30
82
-------
APPENDIX A
TABLE 7
CHRONOLOGICAL DATA
WAXY OIL PRODUCT, "C" PLOTS
1970
pH, Before Extr.
pH, After Extr.
Moisture, %v
Oil, %w
NH, as N, ppm
NO, as N, ppm
J
PO. as P-0 , ppm
4 2. j
Temperature , °F
Ambient
Total 7
Ae robes x 10-
x 10,
xlO7
Number Plowings
Between Sample
Dates
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
APR.
22
7.0
7.0
7.0
17
17
13
10
10
10
Nil
Nil
Nil
Nil
Nil
Nil
110
78
80
MAY
7 13 17 19 27
7.4
7.7
7.4
M
o
8 * 17 9
, 7 5 15 8
7 < 16 10
„ 11 24 22
% 12 20 22
°. 11 19 19
a*
| 440
a. 520
1 Nil
3
2 Nil
£ Nil
•o Nil
0)
3
77 80 83
81 80 82
4
5
2
1 21
JUNE
11 24
6.8
6.8
6.9
8 9
8 8
8 9
22 19
20 16
19 17
50
30
Nil
Nil
Nil
Nil
83 86
82 76
16
41
10
1 1
JULY
10
7.2
7.2
7.2
16
13
12
20
22
17
40
35
Nil
Nil
Nil
Nil
140
105
80
39
128
45
1
29
7.5
6
6
8
19
18
18
3
Nil
Nil
Nil
Nil
Nil
89
87
1
AUGUST
7 14
6.9
6.9
6.8
6
5
5
2 18
1 "
1 17
CO
1 1230
770
a Nil
OS
o Nil
3 Nil
•o Nil
0
•o
< 470
160
89 94
86 86
31
25
4
2
27
6
6
5
17
15
16
94
83
1
83
-------
APPENDIX A
TABLE 7 (CONTD.)
CHRONOLOGICAL DATA
WAXY OIL PRODUCT, "C" PLOTS
1970
SEPT.
pH, Before Extr.
pH, After Extr.
Mois ture » %v
Oil, Zw
NH, as N, ppm
j
NO. as N, ppm
J
PO as P 0 , ppm
H tf J
Temperature, °F
Ambient
Total
Aerobes x 10,
A 10J
x 10
Number Plowings
Between Sample
Dates
C-l
C-2
C-3
C-l
C-2
C-3
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
10
7.0
7.0
7.0
5
6
16
14
15
380
65
Nil
Nil
Nil
Nil
92
82
5
22
6.6
6.9
7.0
4
4
15
13
15
180
20
Nil
Nil
Nil
Nil
88
83
74
44
67
0
OCT.
16
6.5
6.7
7.0
7
5
14
13
16
115
10
Nil
Nil
Nil
Nil
720
360
68
62
3
31
9
7
12
13
14
62
65
87
19
10
3
NOV.
14
6.7
6.9
7.1
6.6
7.0
8
10
13
12
13
Nil
Nil
Nil
Nil
Nil
Nil
700
320
135
63
60
110
93
38
3
DEC.
17
6.2
6.6
7.0
6
5
13
12
14
20
5
Nil
Nil
Nil
Nil
780
295
58
61
49
34
7
5
JAN.
6
6.2
6.6
7.0
7
6
13
12
14
20
10
Nil
Nil
Nil
Nil
880
270
125
43
38
80
66
15
2
27 2
6.4
6.7
6.9 rt
Q
' 1
5 |
12
12
14
en
O
•z. si
-3- (0
93 O
O
•a a.
•8 *
3 §
780
280
140
64 57
62 55
60 53
60 43
3
1971
FEB.
12 24
6.6
7.0
6.9
•\F\ Q
J.U 7
11 10
9 8
31 33
29 31
27 28
460
310
Nil
40
30
Nil
720
250
150
59 82
58 63
58 63
58 65
17
7
4
4 2
MARCH
10
6.7
6.9
7.1
12
9
29
30
29
460
290
Nil
15
13
Nil
650
210
105
68
68
68
70
34
41
130
1
24
i \
J..3
10
5
27
27
28
70
82
70
58
2
84
-------
APPENDIX A
TABLE 7 (CONTD.)
CHRONOLOGICAL DATA
WAXY OIL PRODUCT, "C" PLOTS
1971
APRIL
pH, Before Extr.
pH, After Extr.
Moisture, %w
Oil, 7.w
NH_ as N, ppm
j
NO 3 as N, ppm
P04 as P205, ppm
Temperature, °F
Ambient
Total
Aerobes x 10,
xlO?
x 10'
Number Flowings
Between Sample
Dates
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
7
6.2
6.5
6.8
4
4
4
25
26
27
325
120
Nil
Nil
Nil
Nil
750
260
110
88
82
80
67
4
1
0.1
2
21
7
7
5
24
25
26
en
-t
I
•o
o
•D
3
94
86
82
75
2
MAY
5
6.6
6.7
6.9
4
4
4
24
26
26
205
65
Nil
90
20
Nil
620
180
90
86
86
82
80
2
19
9
8
3
23
25
29
97
94
90
82
10
10
9
'l
JUNE
2
4
5
4
22
25
27
120
40
Nil
Nil
Nil
Nil
92
90
86
83
1
30
6.8
7.0
7.2
13
14
9
21
23
25
230
130
Nil
2
2
Nil
620
200
90
96
92
90
4
49
135
3
JULY AUGUST
14
6.8
6.9
7.1
5
6
4
21
23
26
110
35
Nil
Nil
Nil
Nil
780
280
90
98
94
92
84
19
20
10
2
28 11
6.3
6.3
6.6
6.5
6.6
6.9
6 13
5 13
5 8
20 21
23 25
26 27
-------
APPENDIX A
TABLE 8
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "A" PLOTS
Legend; Solvent a_ was 1.0 N Ammonium Acetate, pH 7, used for soil analysis at Texas A&M University.
Solvent b_ was 1.4 N Ammonium Acetate in 1 N HC1, at pH 4.29 and the analyses were by atomic absorption.
00
CT>
Component START
in ppm April, 1970
Total
Nitrogen 1500
1300
1600
Sulfur 5000
EXTRACTABLE
WITH SOLVENT
a b
Phosphorus 820 36
Sodium AS 700
Potassium 156 930
Magnesium 1490 2050
_^_
Calcium 3300 26900
Plot
No.
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
DURING
Nov. 13, 1970
Total
2820
2500
2590
1650
EXTRACTABLE
WITH SOLVENT
b
3000
96
146
88
140
140
140
1100
1300
1400
45000
21000
22000
April 21, 1971
Total
EXTRACTABLE
WITH SOLVENT
b
350
1000
510
600
375
210
6850
6700
6700
27500
26500
26250
Sept
Total
3300
3100
3600
3200
2100
1800
2300
2500
3400
END
. 23.
1971
EXTRACTABLE
500
370
430
WITH
a
98
36
21
352
560
550
586
460
236
560
600
560
5900
7300
6550
SOLVENT
b
260
260
360
920
920
740
5750
7250
7120
24800
28000
28000
-------
00
APPENDIX A
TABLE 8 (CONTO.)
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "A" PLOTS
Legend: Solvent c_ was 1 N HC1 used for soil analysis at Texas A&M University.
Solvent d was a 50/50 mixture HC1 and HN03 and the analyses were by atomic absorption.
Component
in ppm
Manganese
Iron
Zinc
Copper
Lead
START
April, 1970
EXTRACTABLE
WITH SOLVENT
c d
692 160
3800 10000
1580 1080
21 180
-
Plot
No.
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
A-l
A-2
A-3
DURING
Nov. 13, 1970
EXTRACTABLE
WITH SOLVENT
d
260
200
270
9750
10000
11500
1000
1140
1150
150
160
160
820
900
920
April 21, 1971
EXTRACTABLE
WITH SOLVENT
d
160
270
130
16500
20000
19800
1200
1560
1640
180
230
200
890
980
1030
END
Sept. 23,
1971
EXTRACTABLE
WITH SOLVENT
c d
146
146
144
1110
1160
1230
685
595
628
37
42
45
-
210
180
240
21500
21500
25300
1200
1500
1220
170
160
170
880
790
920
-------
APPENDIX A
TABLE 9
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "B" PLOTS
Legend: Solvent a was 1.0 N Ammonium Acetate, pH 7, used for soil analysis at Texas A&M University.
Solvent b_ was 1.4 N Ammonium Acetate in 1 N HC1, at pH A.29 and the analyses were by atomic absorption.
00
00
Component
in ppm
Nitrogen
Sulfur
Phosphorus
Sodium
Potassium
Magnesium
Calcium
START Plot
April, 1970 No.
Total
1500 B-l
1300e
1600f B-2
B-3
5000 B-l
B-2
B-3
EXTRACTABLE
WITH SOLVENT
a b
820 36 B-l
B-2
B-3
45 700 B-l
B-2
B-3
156 930 B-l
B-2
B-3
1490 2050 B-l
B-2
B-3
3300 26900 B-l
B-2
B-3
DURING
Nov. 13, 1970 April 21, 1971
Total Total
3050
5000
EXTRACTABLE EXTRACTABLE
WITH SOLVENT WITH SOLVENT
b b
3810
100 500
330
300
140 550
375
210
1000 , 6850
6250
6850
17000 29000
25000
27250
Sept
Total
3300
3000
3300
3600
2400
2000
4000
3800
5300
END
. 23.
1971
EXTRACTABLE
970
280
360
WITH
a
222
35
16
270
238
278
796
484
258
550
490
550
5200
5550
5900
SOLVENT
b
220
210
220
920
520
520
6250
6750
7120
24440
26440
25200
-------
APPENDIX A
TABLE 9 (CONTD.)
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "B" PLOTS
Legend: Solvent £ was 1 N HCl used for soil analysis at Texas A&M University.
Solvent d_ was a 50/50 mixture HCl and HN03 and the analyses were by atomic absorption.
00
vo
Component
in ppm
Manganese
Iron
Zinc
Copper
Lead
START
April, 1970
EXTRACTABLE
WITH SOLVENT
c d
692 160
3800 10000
1580 1080
21 180
-
Plot
No.
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
DURING
Nov. 13, 1970
EXTRACTABLE
WITH SOLVENT
d
180
6250
850
130
780
April 21, 1971
EXTRACTABLE
WITH SOLVENT
d
130
140
150
16500
20500
21800
1700
1640
1460
200
200
180
1090
1150
1230
END
Sept. 23,
1971
EXTRACTABLE
WITH SOLVENT
c d
138
138
150
1140
960
980
387
376
349
10
22
28
-
180
190
160
22600
22600
37600
1250
1090
860
170
150
150
1000
880
830
-------
APPENDIX A
TABLE 10
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "C" PLOTS
Legend: Solvent a was 1.0 N Ammonium Acetate, pH 7, used for soil analysis at Texas A&M University.
Solvent b_ was 1.4 N Ammonium Acetate in 1 N HC1, at pH 4.29 and the analyses were by atomic absorption.
vo
O
Component
in ppm
Nitrogen
Sulfur
Phosphorus
Sodium
Potassium
Magnesium
Calcium
START Plot
April, 1970 No.
Total
1500 C-l
1300
1600 C-2
C-3
5000 C-l
C-2
C-3
EXTRACTABLE
WITH SOLVENT
a b
820 36 C-l
C-2
C-3
45 700 C-l
C-2
C-3
156 930 C-l
C-2
C-3
1490 2050 C-l
C-2
C-3
3300 26900 C-l
C-2
C-3
Nov. 13, 1970
Total
2600
1690
3500
EXTRACTABLE
WITH SOLVENT
b
_
60
59
.
140
140
-
1200
1400
_
20000
22000
DURING
April 21, 1971
Total
EXTRACTABLE
WITH SOLVENT
b
260
280
420
600
440
250
6525
6525
6250
27250
26750
27000
Sept
Total
4200
3500
3000
2500
1900
1900
2700
2200
2200
END
• 23,
1971
EXTRACTABLE
940
280
120
WITH
a
134
38
15
240
246
206
792
554
225
500
630
590
5200
6200
6600
SOLVENT
b
180
220
220
800
720
580
6250
7120
7500
22800
22000
29600
-------
APPENDIX A
TABLE 10 (CONTD.)
TOTAL NITROGEN, SULFUR, PHOSPHORUS, AND METALS CONTENTS FOR "C" PLOTS
Legend: Solvent c_ was 1 N HC1 used for soil analysis at Texas ASM University.
Solvent d_ was a 50/50 mixture HC1 and HN03 and the analyses were by atomic absorption.
vo
Component
in ppm
Manganese
Iron
Zinc
Copper
Lead
START
April. 1970
EXTRACTABLE
WITH SOLVENT
c d
692 160
3800 10000
1580 1080
21 180
-
Plot
No.
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
C-3
DURING
Nov. 13, 1970
EXTRACTABLE
WITH SOLVENT
d
210
200
11250
12500
• 900
900
1AO
150
860
940
April 21, 1971
EXTRACTABLE
WITH SOLVENT
d
100
220
1000
15500
20000
20800
1180
1560
1260
150
170
170
1030
1110
1020
END
Sept. 23,
1971
EXTRACTABLE
WITH SOLVENT
c d
180
162
980
830
842
441
18
48
-
260
250
200
21300
22300
23000
920
1190
1150
140
140
140
900
820
880
-------
APPENDIX A
TABLE 11
OIL AND NUTRIENT PENETRATION DEPTHS INTO SOIL
OIL
0 - 0.5 ft-
2 ft.
4 ft.
6 ft.
NUTRIENT
NH , 2 ft.
J
4 ft.
NO 2 ft.
J»
4 ft.
P205,2 ft.
4 ft.
Start
Midway
End
Start
Midway
End
Start
Midway
End
Start
Midway
End
Midway
End
Midway
End
Midway
End
Midway .
End
Midway
End
Midway
End
1
10
10
12
8
6
7
<0.5
<0.5
<0.5
<0.5
<0.5
NIL
NIL
_
NIL
NIL
240
NIL
A
2
13
13
16
18
11
21
<0.5
<0.5
<0.5
<0.5
<0.5
3
13
15
21
21
13
25
<0.5
<0.5
<0.5
<0.5
<0.5
NIL
NIL
NIL
NIL
150
NIL
1
13
15
25
11
11
15
<0.5
<0.5
<0.5
<0.5
<0.5
96
NIL
NIL
NIL
NIL
NIL
NIL
NIL
160
150
NIL
NIL
B
2
11
14
24
11
11
13
<0.5
<0.5
<0.5
<0.5
<0.5
3
12
16
30
11
16
12
<0.5
<0.5
<0.5
<0.5
<0.5
1
11
12
18
11
12
13
<0.5
<0.5
<0.5
<0.5
<0.5
NIL
NIL
NIL
NIL
NIL
NIL
NIL
190
200
NIL
C
2
12
12
18
11
11
12
<0.5
<0.5
<0.5
<0.5
<0.5
NIL
50
NIL
_3_
ll
14
23
11
16
18
<0.5
<0.5
<0.5
<0.5
<0.5
92
-------
APPENDIX A
TABLE 12
HYDROCARBON TYPE FOR "A" PLOTS
AT START
Residual oil in
soil
Oil added
AFTER 8 MONTHS
Residual oil in
soil
Oil added
A-l
A-2
A-3
After addition A-l
(calculated) A-2
A-3
A-l
A-2
A-3
After addition A-l
(calculated) A-2
A-3
AFTER 14 MONTHS
Residual oil in
soil
AT END (17 MONTHS)
Residual oil in
soil
A-l
A-2
A-3
A-l
A-2
A-3
Sats.
40
40
40
36
16
27
33
44
24
30
35
14
21
35
Basis
Resin
21
21
21
8
50
29
34
5
32
22
18
44
42
26
Oil
Arom.
39
39
39
56
32
44
33
51
44
48
47
A2
37
39
Total
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Sats.
4.0
5.2
5.2
6.2
7.0
7.0
1.8
3.5
5.3
6.3
9.2
10.6
3.8
6.3
8.4
1.7
3.1
6.3
Basis
Resin
2.1
2.7
2.7
2.6
3.1
3.1
5.5
3.8
5.4
6.1
4.5
6.0
5.1
4.6
4.3
5.3
6.3
4.7
Soil
Arom.
3.9
5.1
5.1
7.3
7.9
7.9
3.5
5.8
5.3
8.6
12.4
11.4
7.1
10.2
11.3
5.0
5.6
7.0
Total
10
13
13
17
18
18
11
13
16
21
26
28
16
21
24
12
15
18
93
-------
APPENDIX A
TABLE 13
HYDROCARBON TYPE FOR "B" PLOTS
Percent Weight
Basis Oil
Basis Soil
Sats. Resin Arom. Total Sats. Resin Arom. Total
AT START
Residual oil in
soil
Oil added
After addition
(calculated)
AFTER 8 MONTHS
Residual oil in
soil
Oil added
After addition
(calculated)
AFTER 14 MONTHS
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
B-l
B-2
B-3
40
40
40
18
10
15
26
21
21
21
21
26
39
36
25
27
39
39
39
56
51
49
49
52
100
100
100
100
100
100
100
100
Residual oil in
soil
B-l
B-2
B-3
14
13
21
29
23
23
57
65
56
100
100
100
4.3
4.2
6.7
9.0
7.4
7.4
17.7
20.8
17.9
31
32
32
AT END (17 MONTHS)
Residual oil in
soil
B-l
B-2
B-3
13
17
23
40
33
26
47
50
51
100
100
100
5.2
4.4
4.8
7.9
6.9
7.0
1.7
2.1
4.4
6.3
7.4
8.2
4.3
4.2
6.7
3.3
4.6
6.9
2.7
2.3
2.5
6.6
5.9
5.6
6.6
.5.0
4.3
12.6
11.7
9.2
9.0
7.4
7.4
10.0
8.9
7.8
5.1
4.3
4.7
13.5
12.0
11.4
8.7
6.9
8.3
20.1
19.9
17.7
17.7
20.8
17.9
11.7
13.5
15.3
13
11
12
28
25
25
17
14
17
39
39
35
25
27
30
94
-------
APPENDIX A
TABLE 14
HYDROCARBON TYPE FOR "C" PLOTS
Percent Weight
Basis Oil
Basis Soil
Sats. Resin Arom. Total Sats. Resin Arom. Total
C-l
C-2
C-3
C-l
C-2
C-3
C-l
C-2
AT START
Residual oil in
soil
Oil added
After addition
(calculated)
AFTER 8 MONTHS
Residual oil in
soil
Oil added
After addition C-l
(calculated) C-2
C-3
AFTER 14 MONTHS
Residual oil in C-l
soil C-2
C-3
AT END (17 MONTHS)
Residual oil in C-l
soil C-2
C-3
40
40
40
90
27
38
42
90
51
60
62
34
54
61
21
21
21
Nil
35
26
23
Nil
19
14
10
33
18
13
39
39
39
10
38
36
35
10
30
26
28
33
28
26
100
100
100
100
100
100
100
100
100
100
100
100
100
100
4.4
4.8
4.4
15.2
12.9
11.6
3.5
4.6
5.9
18.8
19.9
18.5
11.7
14.4
16.1
5.8
11.3
14.6
2.3
2.5
2.3
2.3
2.5
2.3
4.6
3.1
3.2
4.6
3.1
3.2
4.4
3.4
2.6
5.6
3.8
3.1
4.3
4.7
4.3
5.5
5.6
5.1
4.9
4.3
4.9
6.6
6.0
6.3
6.9
6.2
7.3
5.6
5.9
6.3
11
12
11
23
21
19
13
12
14
30
29
28
23
24
26
17
21
24
95
-------
APPENDIX B
MICROBIAL ANALYSES
PROCEDURE
Soil sample was mixed thoroughly and one gram was weighed aseptically
and placed in a dilution bottle containing 99 ml saline. The sample
was shaken vigorously for one minute then placed on a rotary shaker
for 25 minutes. At the end of this period the bottle was removed and
one ml was pipetted into another 90 ml saline blank and mixed 30
seconds. One-tenth ml of this sample was pipetted onto the surface
of a nutrient agar plate and spread with a sterile glass spreader.
Further serial dilutions and platings were made of the sample in order
to obtain statistically accurate plates (those with 30-300 colonies).
Duplicate platings were made of each sample.
After four days' incubation at 30 C the plates were counted, and the
four most numerous organisms were isolated for identification. Gram
strains and normal biochemical tests were performed on the isolates
and identification was made through Bergey's Manual of Determinative
Bacteriology.6
Predominant individual organisms determined monthly throughout the
project for "A", "B", and "C" plots are given in following Tables 1,
2, and 3, respectively. A.brief description from literature3*6 of
each predominant organism follows these tables.
96
-------
APPENDIX B
TABLE 1
PREDOMINANT INDIVIDUAL ORGANISMS FOR "A" PLOTS
LEGEND
a = A-l
b = A-2
c = A-3
1970
1971
MICROORGANISM
Achromobacter, Sp
cycloclastes
delmarvae
pestifer
xerosIs
Arthrobacter, Sp
tumescens
Bacillus, Sp
cereus var.mycoides
Corynebacterium, Sp
Flavobacteriura, Sp
aquatile
arborescens
balustinura
breve
diffusum
ferruglneura
lutescens
peregrinum
rhenanum
rigense
solare
Micrococcus, Sp
roseus
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR. MAY JUNE JULY AUG. SEPT.
a t b
abc abc ac
abc
ac be
ab be a
abc abcc
c
be
ab
be ace bee abc aabc
ab abc be a
be
ab
c
be
abc
-------
vo
APPENDIX B
TABLE 1 (CONTD.)
PREDOMINANT INDIVIDUAL ORGANISMS FOR "A" PLOTS
1970
1971
MICROORGANISM
Nocardia, Sp
actinomorpha
alba
corallina
flavescens
maculata
minima
opaca
paraffinae
po lychromogenes
rubroportincta
salmonicolor
Pseudomonas, Sp
aeruginosa
arvilla
boreopolis
crucivlae
dacunhae
denitrificans
effusa
oleovorans
oval is
putida
rathonls
striata
stutzeri
Rhodotorula, Sp
Saccharomyces , Sp
analatus
Sarcina, Sp
barker i
flava
Yeast
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR. MAY JUNE JULY AUG. SEPT.
b a
c t c
ac ab t c be
be
abc
be ab be ac be ac
be a
ac a
ab ab
ac
c a be a ab abc abc t abc c c
a abcc
c
ab abc ab
c
ab ac a
ab ab
b b
ab a
b a- a-
b abc t bbc b
b
a
be bbc abc abbe
-------
VO
VO
APPENDIX B
TABLE 2
PREDOMINANT INDIVIDUAL ORGANISMS FOR "B" PLOTS
LEGEND
e = B-l
h = B-2
c = B-3
1970
MICROORGANISM
Achromobacter, Sp
eyeloclastea
delmarvae
pestifer
xerosis
Arthrobacter, Sp
turoescens
Bacillus, Sp
cereus var.mycoides
CorynebacCerium, Sp
Flavobacterium, Sp
aquatile
arborescens
balustinum
breve
diffusum
ferrugineum
lutescens
peregrinum
rhenanum
rigense
solare
Micrococcus, Sp
roseus
1971
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR. MAY JUNE JULY AUG. SEPT.
be
be
b
c
bee
b
c
be
a
abc
ab
abc ab
be
ac
be
ab
be
ab
bbc
abc
be
bee
abc
abc
abc abc
b b
be
aac
b
aabb
be
-------
o
o
MICROORGANISM
Nocardia, Sp
actinomorpha
alba
corallina
flavescens
maculata
minima
opaca
paraffinae
polychromogenes
rubroportincta
salmonicolor
Pseudomonas, Sp
aeruginosa
arvilla
boreopolis
crucivlae
dacunhae
denitrificans
effusa
oleovorans
ovalis
putida
rathonis
scriata
stutzeri
Rhodotorula, Sp
Saccharomyces, Sp
analatus
Sarcina, Sp
barker!
— flava
APPENDIX B
TABLE 2 (CONTD.)
PREDOMINANT INDIVIDUAL ORGANISMS FOR "B" PLOTS
1970
1971
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR. MAY JUNE JULY AUG. SEPT.
be
abc
ab
b
abc
abc
abc
ab
ab
abc
ab
c abc
abc
abbe
b a
be
c
ab
ac aac
Yeast
bbc b ab
-------
APPENDIX B
TABLE 3
PREDOMINANT INDIVIDUAL ORGANISMS FOR "C" PLOTS
LEGEND
C-l
C-2
C-3
1970
1971
MICROORGANISM
Achromobacter, Sp.
cycloclastes
delmarvae
pestifer
xerosis
Arthrobacter, Sp
tumescens
Bacillus, Sp
cereus var.mycoides
Corynebacterium, Sp
Flavobacterium, Sp
aquatile
arborescens
balustinum
breve
diffusum
ferrugineum
lutescens
peregrinum
rhenanum
rigense
solare
Mlcrococcus, Sp
roseus
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR^ MAY
a c c
a ac
JUNE JULY AUG. SEPT.
ab
ab
be
be
bcc
abc
c
be abc
abcc
be
t
bb
ab
be
be
abc
ab
abc
-------
o
NJ
MICROORGANISM
Nocardia, Sp
actinomorpha
alba
corallina
flavescens
maculata
minima
opaca
paraffinae
polychromogenes
rubroportincta
salmonicolor
Pseudomonas, Sp
aeruginosa
arvilla
boreopolis
crucivlae
dacunhae
denitrificans
effusa
oleovorans
ovalis
putida
rachonis
striata
stutzeri
Rhodotorula, Sp
Saccharomyces, Sp
analatus
Sarcina, Sp
barkeri
f lava
APPENDIX B
TABLE 3 (CONTD.)
PREDOMINANT INDIVIDUAL ORGANISMS FOR "C" PLOTS
1970
1971
MAY JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MAR. APR. MAY JUNE JULY AUG. SEPT.
ab
ab
be
abc
ab
ab
abc ab aab ac
ac
ab be be b c
b c ab b b
a
abc
aabbc a abcc ab be
abbcc
c
abbe ab abbbcc
Yeast
-------
APPENDIX B
MICROBIAL ANALYSES
BRIEF DESCRIPTION OF PREDOMINANT ORGANISMS
Achromobacterium, Sp
cycloclastes
delmarvae
pestifer
xerosis
Arthrobacter, Sp
tumescens
Azotobacter, Sp
agilis
Bacillus , Sp
cereus var.mycoides
Corynebacterium, Sp
Flavobacterium, Sp
aquatile
arborescens
balustinum
breve
dif f us urn
ferrugineum
lutescens
peregrinum
Attacks polysulfide polymer and found in used
oil3
Attack phenol and naphthalene, organic acids
not formed6
Produces acid from glucose, nitrites from
nitrates6
Organic acids from hydrocarbons not formed6
Produces nitrites from nitrates6
Citrates not utilized, nitrates and ammonia not
sole source of N6
Fixes atmospheric nitrogen, gives off C02, opt
temp 25-28C6
Attacks polysulfide polymers, found in jet air
fuel, utilize paraffins but not cycloparaf fins3
Optimum pH 5.2, temp 40 °C, starch, sugar hydro-
lizes and produces acetylmethylcarbonol6
Seldom produces acid, glucose reacts to C02 +
, utilizes paraffin tetradecane3
Acids not developed when nitrogen containing
compounds are in the medium6
pH 6.5 - 7.8, 10-30°C, produce acid from sugar6
Opt temp 30°C6 survive in jet fuel3
20-25°C6,
35° found in sewage6
25-30°C6, attacks polysulfide polymer3
pH 7-7.5 min. 6.5, 22-39°C, decomposes carbo-
hydrates6
30-35 °C
Opens benzene rings, destroys 2,4 dichloro-
phenoxyacetic acid
103
-------
rhenanuro
rigense
solare
Hyphomicrobium, Sp
vulgare
Micrococcus, Sp
roseus
Nocardia, Sp
actinomorpha
alba
corallina
florescens
maculata
minima
opaca
paraffinae
polychromogenos
rubropertineta
salmonicolor
Pseudomonas, Sp
aeruginesa
arvilla
boreopolis
crucivlae
dacunhae
denitrificans
effusa
30°C produces acid from sugar, no reaction with
starch6
30°C produces acid from glucose and starch
hydrolized6
30° C
pH 7-7.5, 20-37°C, utilizes organic acids6
Utilizes paraffins, oxidizes phenols and found
in used oil3
25°C
Highly efficient paraffin to cellular matter
conversion3
pH 7.8 - 8.5, 25-30°C, utilizes phenols and
naphthalene6, oxidizes alkyl cyclic hydrocarbon6
Hydrolizes sugar, starch and organic acids6
pH 6.8 - 8, 22-25°C, utilizes phenol, cresol,
and naphthol6
28-38°C, hydrolizes starch6
Hydrolizes starch6
22-25°C, utilizes paraffin6
pH 6.8 - 7.3, 30°C, utilizes phenol and
naphthalene6
Min. pH 4.4, utilizes paraffin wax6
22-25°C6
pH 6.8 - 7.2, 20-37°C, utilizes benzene,
paraffin and mix petroleum6
20-22°C, utilizes paraffins6
Oxidizes paraffins, cycloparaffins, hydrocarbons,
used oil3, oxidizes hydrocarbons6
37-42°C, oxidizes toluene, asphalt, produces
odor trimethylamine (TMA)6
37°C, attacks naphthalene6
35-37°C, attacks naphthalene6
30-35°C, attacks phenols and m-cresol6
37°C, attacks phenols6
25 °C6
37°C6
104
-------
olevorans
ovalis
putida
rathonis
striata
stutzeri
Rhodotorula, Sp
Saccharomyces, Sp
analatus
Sarcina, Sp
barker!
f lava
Streptomyces, Sp
anulutus
bikinierisis
Yeast
25-37°C, attacks cutting oil and starch6
25-36°C6
25-27°C, putrify material and form TMA6
35°C, attacks phenol, cresol and naphthalene5
25-36°C6
pH 7-9, 35°C, anaerobic N03 to N6
Found in used oil3
pH 7, 30°C, produces methane from carbonic acid6
Utilize paraffins and found in used oil3
Antagonistic mycobacteria
Strongly antagonistic, produces streptomycin
105
-------
APPENDIX C
MICROBIOLOGY CONSULTANT'S COMMENTS
Many studies have been carried out on the identity of organisms
capable of oxidizing hydrocarbons. The results obtained in this
project are very similar to the results obtained in other research
projects.15 The major species present are members of the genus
Pseudomonas, Flavobacterium, Nocardia, Corynebacterium, and Arthro-
bacter.
The nature of the hydrocarbon substrate does not appear to influence
the types of organisms present; however, it does have an effect upon
the number of bacteria in the soil samples. Generally, the same types
of organisms predominated in the three plots. Crude oil tank bottom
sludge produced the highest counts, the waxy oil product produced
intermediate counts, while bunker C fuel exhibited the lowest
microbial population.
Some evidence of ecological progression was noted during the 18-month
test period. Members of the genera Achromobacter and Arthrobacter
were present in the early stages of the project but gradually dis-
appeared from the plots. These genera were generally absent from all
plots during the second half of the study. Members of genus Coryne-
bac terium began to appear at about the same time as Achromobac ter and
Arthrobacter species disappeared from the soil samples. Members of
the genera Flavobacterium, Nocardia, and Pseudomonas were generally
present throughout the test period. Unidentifiable yeasts began to
invade the test plots during the last three months of the project.
The presence of Bacillus, Sarcina, and Streptomyces species is prob-
ably not significant and has no relationship to the disposal of hydro-
carbons. These organisms may have invaded the plots at variable
times due to dust contamination of the plots. The dust may have come
from other areas.
Temperature appeared to have no effect upon the organisms present.
Some of the highest counts were obtained during the winter months.
106
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APPENDIX C
TABLE 1
STATISTICS OF MICROBIAL ANALYSIS
PERCENT TIMES ISOLATED FROM SAMPLES
Genus
Ps eudomonas s p .
Flavobacterium sp.
Nocardia sp.
Corynebacterium sp.
Arthrobacter sp.
Unidentified yeasts
Sac char omyces sp.
Micrococcus sp.
Achromobacter sp.
Rhodotorula sp.
Sarcina sp.
Bacillus sp.
Streptomyces sp.
A
88.8
72.2
77.7
38.8
31.4
22.2
16.6
9.2
9.2
5.5
3.7
3.7
1.8
Plots
B
72.2
92.5
62.9
53.7
25.9
14.8
9.2
16.6
16.6
9.2
3.7
1.8
3.7
C
94.4
61.1
77.7
33.3
14.8
27.7
18.5
16.6
12.9
3.7
9.2
3.7
3.7
Mean
85
75
72
41
24
21
14
14
12
6
5
3
3
107
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APPENDIX C
MICROBIOLOGY CONSULTANT REPORT
Report of sampling of plots B-2 and C-2 with comparison counts on N.A.
and 17<> H.C. in nutrient agar media.
B-2 - 1% #6 Fuel oil
C-2 1% Paraffinate oil
Nutrient Agar Fuel
31~X 106 cells/gm 17~X 106 cells/gm
Co c* *y
™ S \J ~ £,
~T~X 106 cells/gm Ti~X 105 cells/gm
Organisms - N.A.
B-2 Flavobacterium lutescens
Corynebacterium
Yeast IV
Co ryneb ac t e r ium
C-2 Yeast I
Yeast II
Yeast IV
Corynebacterium
Hydrocarbons
B-2 Only three isolated, checked for characteristics by streaking
on N.A. plate
Corynebacterium sp. I
Corynebacterium sp. II
Yeast sp. IV
C-2 Only three org. isolated
Corynebacterium sp. IV
Pseudomonas sp. (unlike others)
Yeast sp. Ill
108
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APPENDIX D
INFRARED STUDY OF OILS EXTRACTED FROM SOIL
Method Summary
The infrared (IR) spectra of diluted oil samples were obtained on a
Perkin-Elmer, Model 137, double-beamed spectrophotometer. Wavelength
accuracy is ±0.03 microns. The oils were examined in matched NaCl
absorption cells of 0.5 mm thickness.
The oil samples were prepared for IR scans by first dissolving a small
portion of the oil in carbon tetrachloride (CC14). The sample was then
centrifuged in a high-speed unit (5000 rpm) to remove very fine parti-
cles of soil entrained during the original extraction of the soil. The
solvent was evaporated from the decanted solution under a nitrogen
atmosphere at 250°F. Two solutions were prepared gravimetrically for
scanning. The 2.0 to 9.0 micron (y) region was scanned on a 4%w/v
CCl^ solution, and the 8.5y to 15.Op region was scanned on a 10%w/v
carbon disulfide (€82) solution. Solvent absorption was cancelled by
scanning the solvent simultaneously in the reference beam of the
spectrophotometer.
IR Band Assignments
The various structures from which the IR absorption bands arise are
noted at the bottom of each of Figures 25-27. These assignments are
well known but require some explanatory comments. The absorption near
2.9y is assigned to OH groups other than those in organic acids. This
absorption could also arise from NH groups; however, such materials
are not present in waxy raffinate, yet the 2.9y band is the most
prominent in this material. The absorption intensity of this band in
all of the samples is weak and appears to vary randomly. Since no
special steps were taken to dry the oil samples or exclude small
amounts of moisture during handling, the 2.9y band may arise from
small amounts of water. No further consideration will be given to
this band.
There are four absorption bands that have been assigned to organic
acids. The OH portion of the carboxyl group (COOH), when present as
the dimer, exhibits a broad absorption on the long-wavelength side of
the strong CH absorption band. This absorption is weak and difficult
to see at low concentrations of organic acids.
The sharp absorption band at 5.85y has been attributed to the C=0 of
the acid group. This assignment has been verified by examination of a
single oil sample in p-dioxane solution resulting in a shift of the
C=0 band to 5.75y. The effect of polar solvent alone should produce a
shift of the band to longer wavelength. The shift of the C=0 band in
109
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question to a shorter wavelength is indicative of dissociation of the
acid dimer. Moreover, the actual shift to a shorter wavelength is less
than would have been predicted by about the amount of reverse shift
expected from the polar solvent. This prediction is based on Silver-
stein, R.M., and Bassler, G.C., Spectrometric Identification of Organic
Compounds, Second Edition, John Wiley and Sons, Inc., New York, 1967.
The assignment has been further verified by treating the oil sample
with triethylamine in chloroform solution. This treatment resulted in
a shift of the C=0 band to about 6.3y by conversion to the carboxylate
ion, and the occurrence of a new band at 4.05y indicative of the
"ammonium band", also described by Silverstein and Bassler.
The absorption bands at 7.75y and 10.6y are assigned to the acid C=0
stretching band and the OH bending of the dimer, respectively. At first
glance, absorption will be noted in the 7.65 7.75y range in all of
the samples including the waxy raffinate. Absorption at 7.65y is
attributed to saturate groups; however, careful examination will reveal
that, in those samples where the acid C=0 absorption is strongest, this
weak band is shifted to 7.75y and becomes more pronounced.
The absorption band near 6.2y is assigned to C=C groups in aromatic
structures. This band can be used as a gross measure of aromatic con-
tent, but widely varying intensities among aromatic types limits its
usefulness for quantitative measurements.
The absorption bands at 6.85y and 7.25y are assigned to CH2 and CH3
groups, respectively. It should be pointed out that these bands
include such groups in both saturate molecules, per se, and in alkyl
appendages on aromatic nuclei. The band at 13.88y is the well known
absorption arising from long paraffin chains; i.e., where four or more
CH2 groups are linked together in an uninterrupted sequence. Again, a
five carbon sequence attached to an aromatic ring would also qualify.
The three strong absorption bands near 11.4y, 12.2y, and 13.2y all
arise from aromatic structures. The structures shown on the figures
are intended only to illustrate the different configurations of the
hydrogen atoms around the aromatic nucleus, as these absorption bands
actually arise from the in-phase, out-of-plane vibrations of the
hydrogen atoms. The position of the bands are actually dependent upon
the number of hydrogen atoms that are adjacent to each other, and the
aromatic nucleus can be a single or multi-ring system. Thus, in a
polyaromatic ring system such as H , where all
hydrogen vacancies are occupied by R groups, all three configurations
of hydrogen atoms are present.
110
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Results
The three different types of oils added to the soil test plots in the
demonstration of oily waste disposal by the soil cultivation process,
oil extracted from the soil at the start of the project, and oils ex-
tracted from the soil at the end of eight months (midway) and again at
the end of the experiment (after 17 months), were examined by infrared
spectroscopy. In between the 8-month and 17-month sampling periods,
additional oils were added to the plots. The spectra of the oil samples
where crude oil tank bottoms was added to the soil plots are designated
as "A" plots and are shown in Figure 25. The "B" plots received bunker
C oil (No. 6 fuel oil) and are shown in Figure 26. The "C" plots
which were treated with waxy raffinate are shown in Figure 27.
Different degrees of fertilization, which was a principal variable in
the experiment, are noted on the figures.
Oil Residue in Soil
The IR spectrum of the oil extracted from the soil at the beginning of
this study is repeated in each figure for convenience, and has the
gross character of a polyaromatic oil. Considerable evidence of
saturate groups is observed at 6.85y and 7.25y together with a small
amount of long chain paraffin groups at 13,88y. The weak C=0 band at
5.85y indicates a small amount of organic acids. The other organic
acid bands are not apparent, but treatment of this oil with tri-
ethylamine confirmed the presence of acid C=0 structures.
"A" Plots, Figure 25
The IR spectrum of the crude oil tank bottoms is typical of a saturate-
aromatic oil mixture. The aromatic content is probably less than that
in the oil extracted from the soil originally. This oil appears to
contain simpler aromatic structures as evidenced by the differences in
the ll-14y region. As expected, there is no evidence of CO structures.
The gross aromatic character of the oils extracted from all of the "A"
plots are similar to that of the original oil extracted from the soil,
indicating that the remaining oil in each case was more polyaromatic.
There does not appear to be any significant effect of fertilizer upon
the aromatic structures.
There is evidence of a small amount of long chain paraffin groups at
13.88y, but the amount diminishes as the degree of fertilization is
increased. After 17 months there is still some evidence of paraffin
chains.
The most significant differences among the oils from the "A" plots are
found in the organic acid content. After 17 months there is only a
small amount of C=0 structure in A-3, and the absorption for saturate
groups at 6.85y and 7.25y are still quite strong. A-2 shows a large
111
-------
increase in C=0 band intensity and the other acid absorption bands are
evident. There is a further small increase in organic acids in A-l,
and the saturate groups at 6.85y and 7.25y decrease in both A-l and A-2
as the organic acid groups increase. There is little difference in the
results obtained on the samples from the "A" plots after eight months,
except that the increase in organic acids was not as great with
moderate fertilization as was observed for the sample after 17 months.
"B" Plots, Figure 26
The IR spectrum of the bunker C oil is typical of a polyaromatic oil
and is quite similar to the oil extracted originally from the soil,
except that there is less long chain paraffin content and an absence
of organic acids.
After eight months' residence time, the aromatic characteristics of the
oils from the "B" plots are quite similar and also similar to the
original oil extracted from the soil. The results are similar to
those in the "A" plots in that the long chain paraffin band is small .
and decreases with increased degree of fertilization. The organic acid
content is evident but low in the spectrum of B-3; the other spectra
show a progressive increase in plots B-2 and B-l as the amount of
fertilizer was increased. There is a concomitant decrease in the
saturate groups at 6.85y and 7.25y with the increase in organic acids.
After 17 months, the IR spectra of the oils from the "B" plots indi-
cate that something unique has occurred, since the organic acid content
does not appear to increase in those plots where fertilizer was applied.
There is also little change in the long chain paraffin groups in going
from plots B-3 to B-l. An explanation for these results is offered in
the body of this report.
The absorption at 9.65y, attributed originally to aromatic materials,
shows a broadening and an increase in intensity in the spectra of the
original bunker C oil and also of plot B-2 after 17 months. This
behavior is probably due to contamination by traces of dirt particles
as silicas display absorption in this region of the IR spectrum.
"C" Plots, Figure 27
The IR spectrum of the waxy raffinate is typical of a nonaromatic oil.
There is evidence of a very small amount of aromatics near 6.2y. How-
ever, the principal absorption arises from the saturate groups at
6.85y and 7.25v and a large concentration of long paraffin chains at
13.88y.
Oil extracted from each of the "C" plots is similar to that of the
original oil in the soil. The spectra are typical of polyaromatic oils
even though the added oil was principally paraffinic. This is not to
suggest that the paraffin oils are converted to aromatics, but that
112
-------
the paraffinic portion of the added oils was largely decomposed, even
in the absence of fertilizer.
The amount of long chain paraffins remaining after 17 months in the
unfertilized plot (C-3) was greater than that after eight months as
evidenced by the 13.88y band intensity. There .was a higher concentra-
tion of long chain paraffins in both C-3 plots than in the oil present
originally in the soil, indicating that some paraffin material survived
the 17 months' residence in the soil. The amount of paraffinic
material appeared to diminish in those plots where fertilizers were
used.
The use of fertilizer enhanced the production of organic acids in pro-
portion to the amount of fertilizer used as evidenced by the increased
CO band intensity at 5.85y. The increase with moderate amounts of
fertilizer was greater in the eight months sample. A significant
decrease in saturate groups at 6.85p and 7.25y parallels the increase
in organic acid C=0 structures. The organic acid content was quite
low in C-3 after 17 months but greater in C-3 after eight months.
This difference inversely paralleled the change in long chain paraffin
content as would be expected.
INFRARED STUDY OF RAINFALL RUNOFF WATER
Infrared spectra of the oils recovered from samples of runoff water by
CClij extraction were obtained as conventional scans on the neat oils
following the evaporation of the solvent.
Three nonvolatile oils (NVO) and two volatile oils (VO) recovered from
samples of runoff water were selected for IR examination. These oils
included NVO from plots A-l, B-l, and C-l, and VO from plots A-2 and
C-l. The IR spectra of all of the oils were very similar and were
identified as naphthenic acid concentrates by comparison with an IR
spectrum of a naphthenic acids mixture obtained from Eastman Kodak
Company. This identification has been confirmed from examination of
the NVO from plots A-l and C-l by high-resolution mass spectiometry,
which shows that both samples are very similar and that they consist
of mixtures of naphthenic acids in the 200-300 molecular weight range.
Small amounts of other saturated organic acids may be present.
The long chain paraffin based at 13.88 per is absent from the IR
spectra in all but one of the oils (VO from plot C-l), and no sig-
nificant amounts of aromatics are seen in any of the oil. Ultraviolet
(UV) spectra of NVO from plots A-l and C-l (other oils were not
examined by UV) are completely lacking in characteristic UV absorp-
tion, and thus tend to confirm the absence of significant amounts of
aromatic structures.
113
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APPENDIX E
OIL CONTENT IN SOIL SAMPLES
Modified ASTM Method D-473,
"Sedimentation in Fuel Oil by Extraction"
Modifications of ASTM method D-4738 were made to adapt the method for
determination of oily matter in soil. A change in the apparatus con-
sisted of a stainless steel wire cone in place of the extraction
thimble of D-473. A sketch of the modified apparatus is attached. For
the test, a folded filter paper placed inside the cone held a weighed
quantity of soil in a position beneath the condenser coil such that
solvent condensate (condensed vapors) trickled through the soil and
accomplished the extraction of oil from the soil. The solvent was
carbon tetrachloride, C.P. grade, and the source of heat was an
electrical heater (Ful-Kontrol, 750 watts).
The procedure included 1) placing a weighed soil sample inside the
filter-paper lined, conical-wire basket, 2) drying the soil by placing
the basket in an oven at 110°C for one hour, and 3) weighing the dry
soil before extraction of the oil. The difference in weight before
and after drying was considered to be water. The dried weighed soil
was then placed in the extraction flask and extracted with carbon
tetrachloride according to D-473 method procedure. After a period of
two to three hours, and/or when the drops from the bottom of the wire
basket appeared colorless, the heater was turned off and the sample
allowed to cool. Then the condenser was removed and the carbon tetra-
chloride was evaporated, leaving the oily residue in the flask. Final
evaporation was accomplished by introducing a stream of nitrogen gas
into the heated oil-containing flask. Heat lamps were used for this
final step. The flask containing the oil was weighed, then the oily
residue was washed from the flask with carbon tetrachloride and a tare
weight of the dry flask without the oil was obtained.
An alternate method was to oven-dry the soil sample after the extrac-
tion step and obtain the weight of the dry, oil-free soil.
For oily soil samples containing volatile components at the initial
drying temperature of 110°C, the undried soil sample was weighed and
extracted with carbon tetrachloride. The extracted soil was then oven
dried and the difference in the initial weight and final weight was
the total oil plus water. Oil was determined from the differences in
the flask weights by the above described procedure and the water con-
tent was calculated by difference.
114
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APPENDIX E (CONTD.)
COOLANT
STAINLESS STEEL
WIRE BASKET
SOLVENT
APPARATUS FOR EXTRACTION OF OIL IN SOIL
115
OU.S. GOVERNMENT PRINTING OFFICE:1973 514-151/137 1-j
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1
Accession Number
w
5
2
Subject Field & Group
10A
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Organization
OIJT7T T OTT rnvCDAVTV UnTTCTY^M CTTPTNTi'PV
DEER PARK, TEXAS
Title
OILY WASTE DISPOSAL BY SOIL CULTIVATION PROCESS
1 Q Authors)
Kincannon, C. Buford
16
21
Project Designation
EPA, Project No.
12050 EZG
Note
22
Citation
Environmental Protection Agency report
number EPA-R2-72-110, December 1972.
23
Descriptors (Starred First)
*0il Waste, *Sludge Treatment, *Soil Disposal Fields, *Soil Microbiology, *Sludge Di:
posal, Disposal, Soils Oil Industry, Oil, Water Pollution Sources, Industrial Waste, Waste;
Bacteria, Decomposing Organic Matter, Biodegradation, Waste Disposal, Microorganisms,
Aerobic Bacteria, Soil Bacteria Pseudomonas Fertilization, Drainage Effects, Fertilizers,
Soil Treatment Nutrient Requirements, Ammonium Compounds, Nitrates, Phosphates, Potash,
Ureas, Chromatography, Separation Techniques, Solvent Extraction Fertilizer.
25
Identifiers (Starred First)
Arthrobacter, Corynebacterium, Flavobacterium, Nocardia, Infrared Adsorption
Oil Analyses
27
Abstract
Three oily materials were used in parallel experiments to demonstrate oily waste dis
posal by a soil cultivation process at prevailing climatic conditions. The 18-month exper:
ments conducted with nine soil test plots at Deer Park, Texas, showed average oil decompos:
tion rates of 0.5 Ibs/ft^ of soil per month without fertilizers and about 1.0 Ib/ft^/month
when fertilized. Results of semi-monthly oil determinations for each plot are given. Maj<
microbial species active in the soil were members of the genus Arthrobacter, Corynebacterii
Flavobacterium, Nocardia, and Pseudomonas. Predominant species in each soil test plot are
reported on a monthly basis.
Differences in decomposition rate and microbial species due to hydrocarbon type as
present in the three feedstocks, i.e., crude oil, bunker C fuel oil, and waxy raffinate oi
were minimal. Infrared and gas chromatography examinations of oil extracted from fertiliz<
and unfertilized soils showed differences in organic acid contents and boiling ranges.
Oil and fertilizer chemicals did not infiltrate vertically into the soil at the test
location under prevailing conditions.
Rainfall runoff water contained 1) up to 100 ppm extractable oils found to be naph-
thenic acids and 2) up to 150 mg/1 ammonia as N when the nitrogen nutrients were excessive
in the soil.
Photographs show preparation of soil test plots, spreading of oil on the soil, and
cultivation. Data are tabulated and shown graphically. (Kincannon-Shell)
Abstractor
C. Buford Kincannon
Institution
SHELL OIL COMPANY
WR:I02 (REV. JULY 1969)
WRSIC
SEND, WITH COPY OF DOCUMENT, TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 20240
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