PB85-166353
Land Treatment of an Oily Waste—
Degradation, Immobilization and Bioaccumulation
Cornell Univ., Ithaca, NY
Prepared for
Robert S. Kerr Environmental Research Lab,
Ada, OK
Feb 85
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
NTIS
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PB85-166353
EPA/600/2-85/009
February 1985
LAND TREATMENT OF AN OILY WASTE-
DEGRADATION, IMMOBILIZATION AND BIOACCUMULATION
Raymond C. Loehr
John H. Martin, Jr.
Edward F. Neuhauser
Roy A. Norton
Michael R. Maleckl
Department of Agricultural Engineering
Cornell University
Ithaca, New York. 14853
Project CR-809285
Project Officer
John Matthews
Robert S. Kerr Environmental Research Laboratory
P.O. Box 1198
Ada, Oklahoma 74820
Robert S. Kerr Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Ada, Oklahoma 74820
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
' TpAR/GO°0/2-85/009
4 TITLE AND SUBTITLE
Land Treatment of an Oily Waste—Degradation,
Immobilization and Bioaccumulation
3. RECIPIENT'S ACCESSION NO.. _
a MtfOHT DATE
February 1985
6. PERFORMING ORGANIZATION CODE
7 AUTHOH(S)
R. C. Loehr, J. H. Martin, E. F. Neuhauser,
R. A. Norton, and M. R. Malecki
8 PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Department of Agricultural Engineering
Cornell University
Riley-Robb Hall
Ithaca, NY 14853
10 PROGRAM ELEMENT NO.
5ABW63LOCO (Obj. Class 2401)
11 XBjgXHRKBS»*«XJt#> Coop. Agr.
CR809285
12 SPONSORING AGENCY NAME AND ADDRESS
R. S. Kerr Environmental Research Laboratory
U. S. Environmental Protection Agency
P. 0. Box 1198
Ada, OK 74820
13. TYPE OF REPORT AND PERIOD COVERED
Final 09/31 - 12/84
14 SPONSORING AGENCY CODE
EPA/600/15
IS. SUPPLEMENTARY NOTES
16. ABSTRACT ^j^ industrial oily waste was applied to field plots in New York to determine
loss and Immobilization of waste constituents and to determine impact of waste on soii
biota. Four replicate plots were established for natural controls, rototilled contro:
and low, medium and high application rates. Wastes were applied 06/82, 10/82, and
06/83. In 06/83, plots that had previously received low applications received a very
high application. During the study, waste was-applied to test plots at seven loading
rates that ranged from 0.17-0.5 kg total oil/m or from 0.09 wt%-5.25wt% oil in soil.
Waste application increased soil pH and volatile matter. Half life of total oil
in field plots ranged from about 260 to 400 days. Not all of the applied oil was lost
The refractory fraction ranged from 20% to 50% of applied oil. The fraction did not
appear to adversely affect soil biota. Napthalenes, alkanes and specific aromatics
were lost rapidly, especially in warmer months. The half life generally was less thai
30 days.
Waste applications increased the concentration of several metals in the upper 15
cm of soil. Earthworms bioaccumulated Cd, K, Na and Zn. Accumulation could not be
related to waste application and occurred in worms from control plots as well as
those receiving waste. Earthworms did not accumulate the specific waste organics.
Waste application reduced numbers and biomass of earthworms and numbers and kinds of
microarthropods; however, both types of soil biota were able to recover.
s,
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Industrial waste
Land treatment
Oily waste
.b.IDENTIFIERS/OPEN ENDED TERMS
Soil biota
Degradation
Immobilization
Bioaccumulation
c. COSATI Held/Group
13B
13. DISTRIBUTION STATEMENT
Release to public
19 SECURITY CLASS (ThisReport/
Unclassified
21 NO. OF PAGES
142
20 SECURITY CLASS (Thispage/
Unclassified
22. PRICE
EPA Form 2220-1 (9-71)
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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FOREWORD
EPA is charged by Congress to protect the Nation's land, air, and water
systems. Under a mandate of national environmental laws focused on air and
water quality, solid waste management and the control of toxic substances,
pesticides, noise, and radiation, the Agency strives to formulate and' imple-
ment actions which lead to a compatible balance between human activities and
the ability of natural systems to support and nurture life.
The Robert S. Kerr Environmental Research Laboratory is the Agency's
center of expertise for investigation of the soil and subsurface environment.
Personnel at the Laboratory are responsible for management of research pro-
grams to: (a) determine the fate, transport and transformation rates of
pollutants in the soil, the unsaturated zone and the saturated zones of the
subsurface environment; (b) define the processes to be used in characterizing
the soil and subsurface environment as a receptor of pollutants; (c) develop
techniques for predicting the effect of pollutants on ground water, soil and
indigenous organisms; and (d) define and demonstrate the applicability and
limitations of using natural processes, indigenous to the soil and subsurface
environment, for the protection of this resource.
This project was initiated to determine: (a) the loss and accumulation
of oily waste constituents when applied to land in the cool and humid northeast,
(b) the impact of single high waste-soil loading rates, and (c) the impact of
waste application of soil biota. Results indicate that organic constituents
would be lost and metal constituents would accumulate in the zone of incorpor-
ation at all of the loading rates used during the study. Both the loss and
accumulation rates varied for different constituents. The soil biota was
impacted at all loading rates; however, the degree of impact and time for
recovery was dependent on the waste application rate. This information should
prove useful to those responsible for regulating, designing, operating and
monitoring industrial waste land treatment systems.
Clinton W. Hall
Director
Robert S. Kerr Environmental
Research Laboratory
iii
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ABSTRACT
The land treatment of an industrial oily waste was investigated to
determine the loss and immobilization of constituents in the waste and to
determine the impact of the waste and the application process on the soil
biota. The project was a field study with laboratory components.
The waste was applied to field plots of a moderately to slowly per-
meable heavy silt loam in New York. The field plots consisted of four
replicates each of natural controls, rototilled controls, and low, medium
and high application rate plots. Wastes were applied in June 1982,
October 1982 and June 1983. In June 1983, the plots that had received the
low applications received a very high application and became the very high
application plots. During the study, the waste was applied to the test
plots at seven waste application rates that ranged from 0.17 to 9.5 kg
total oil and grease/meter^ or from 0.09% to 5.25% oil and grease in the
zone of incorporation.
The application of the wastes increased the pH and volatile matter of
the soils. Over the period of the study, the half life of the total oil
and grease in the field plots ranged from about 260 to about 400 days.
Not all of the applied oil was lost from the plots. The refractory frac-
tion ranged from 20% to an apparent 50% of the applied oil and grease.
The refractory fraction did not appear to adversely affect the soil biota.
Napthalenes, alkanes and specific aromatics were lost from the soil
rapidly, especially in the warmer months. The half life of these
compounds generally was less than 30 days.
The waste applications increased the concentration of several metals
in the upper 15 cm of the soil. Except for sodium, all of the metals were
immobilized in the upper 15 cm of the plots.
Earthworms bioaccumulated cadmium, potassium, sodium and zinc. The
accumulation could not be related to waste application rates and occurred
in worms from the control plots as well as in worms from the plots that
received Che wasces. The land treatment of these wastes did not cause any
unexpected bioaccumulatlon of metals in the earthworms. The earthworms
did not accumulate napthalenes, alkanes or specific aromatics that were in
the applied waste.
Rototilling and waste application reduced the numbers and biomass of
earthworms and the numbers and kinds of mlcroarthropods In the field
plots. Both types of soil biota were able to recover from the rototilling
and waste application.
iv
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This report was submitted in fulfillment of Cooperative Agreement
CR-80928S between Cornell University and the U.S. Environmental Protection
Agency. This report covers the period of September 1981 through September
1984. All field and laboratory work was completed as of August 1984.
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CONTENTS
Disclaimer n
Abstract lv
Contents vl
Figures vii
Tables ix
L. Introduction 1
Background 1
Objectives and Scope 3
2. Conclusions 4
3. Experimental Procedures 6
General 6
Waste Characteristics 6
Field Site 7
Analytical Procedures 10
Special Studies 17
4. Laboratory Studies 18
5. Field Study 26
Waste Application 26
Climatic Data 26
Soil Characteristics 30
Earthworm Data 59
Microarthropods 74
References 82
Appendices • 85
vi
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FIGURES
Numbei
1
2
3
4
5
Schematic of the plots used in the field study ......
Methodology used to determine the impact of wastes on
Toxicity of the oily waste in the artificial soil test . .
Worm biomass and cocoon production in the growth and
Page
11
12
16
20
reproduction tests 21
6 The impact of soil from the field plots on earthworm
survival using the artificial soil test 24
7 Monthly precipitation at the field site 28
8 Monthly average soil and air temperatures at Ithaca, NY . 29
9 Mean value of pH, volatile matter and TKN in the soil
of the field plots, n = 4 31
10 ' Effect of the June 1983 very high waste application
on the mean value of soil pH, n = 4 32
11 Average oil and grease concentrations in the soil
of the field plots 34
12 Average oil and grease concentrations in the soil of
the very high application field plots 35
13 Average oil and grease concentrations in the soil of
the high application field plots 36
14 Temperature of soil in the field plots during Che study . . 41
15 Soil temperatures in the natural control and very high
application plots - 1983-1984 42
16 Average soil moisture in the field plots - 1982-1984 ... 43
vii
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Number Page
17 Chromium and copper concentrations in the soils of the
field plots 48
18 Nickel and zinc concentrations in the soils of the
field plots 49
19 Chromatograms of organics extracted from the soil of
Plot 5 - a very high application plot 55
20 Chromatograms of organics extracted from the soil of
Plot 12 - a very high application plot 56
21 Mean values of worm biomass found in the field plots . . . 60
22 Mean values of the numbers of earthworms found in the
field plots 61
23 Comparison of earthworm biomass and soil temperature
in the field plots 64
24 Comparison of earthworm bionass and soil moisture in
the field plots 65
25 A. general conceptual model of the impact to and recovery
of soil biota when wastes are applied to the soil ... 66
26 Mean total microarthropods (mites and collembolans)
collected at the field plots — data transformation
is Iog10(n+l) 78
viii
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TABLES
Number Page
1 Average characteristics of the oily waste applied to
the field plots 7
Average concentrations of metals in the oily waste
applied to the field plots, mg/kg MFB*
3 Organic compounds in the oily waste applied to the field
plots 9
4 Field study measurements 14
5 Methods used for analysis of waste and soil samples .... 15
6 Results of the artificial soil test using soil obtained
from specific plots on the noted sampling dates '23
7 Field plot study application rates, kg/m2 27
8 Total oil and grease loss in the field plots 37
9 Maximum estimated oil and grease loss in the field plots . 39
10 Average CEC values for the soils at the field site .... 44
11 Percent increase"1" in soil metal concentrations as a
result of the waste applications 45
12 Statistical analysis* of the changes** in soil metal
concentrations (0-15 cm) after the waste applications . . 47
13 Average chromium and zinc concentrations'*" in the top 15
centimeters of the soil of the field plots —
statistical analysis* 50
14 Average copper and lead concentrations"1" in the top 15
centimeters of the soil,of the,field plots —
statistical analysis* 51
15 Metal concentrations* in subsurface soils (15 to 30 cm
depth) at the field plots 52
ix
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Number Page
16 Estimated loss of organic compounds in the field plots"1" . 57
17 Average chromium and zinc concentrations"1" in the earth-
worms of the field plots — statistical analysis* .... 68
18 Average copper and lead concentrations'*" in the earth-
worms of the field plots — statistical analysis* .... 69
19 Statistical evaluation"1" of the earthworm metal concen-
trations during the project period (F values) 71
20 Bioaccumulation"1" of metals by earthworms++ 72
21 Earthworm bioaccuraulation factors for cadmium, copper,
lead and zinc* 73
22 Earthworm bioconcentration factors for several metals*. . 74
23 Soil microarthropod sampling dates 75
24 Total numbers of microarthropods collected at the field
plots during June 1982 to July 1983 77
25 Microarthropods in the field plots expressed as % of
natural control plot numbers* 77
26 Impact of rototilling and oily waste application on
microarthropod species in field plots 79
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SECTION 1
INTRODUCTION
BACKGROUND
Land treatment is a managed waste treatment and ultimate disposal
process that involves the controlled application of a waste to a soil.
The wastes are applied to the surface or mixed with the upper zone (0-1
ft. (0-0.3 m)) of soil. The objective of land treatment is the biological
degradation of organic waste constituents and the immobilization of
inorganic waste constituents. In this way, the assimilative capacity of
the soil is utilized for waste management. Municipal wastewaters and
sludges as well as industrial wastes can be treated using this process.
Land treatment should not be confused with: (a) the indiscriminate
dumping of waste on land, (b) landfills, (c) deep well injection or (d)
arid region waste impoundments. The design goals, long term impact, and
degree of treatment of these other terrestrial systems are different from
those of land treatment.
The performance of a land treatment site is a function of the dynamic
physical, chemical, and biological processes that occur in the soil. As a
result, the applied wastes are degraded, transformed and/or immobilized.
These processes are similar to those that occur in conventional municipal
and industrial waste treatment systems. One major difference is that with
land treatment, the processes occur in an unconfined reactor filled with
soil while with conventional systems the processes occur in tanks.
Another major difference is that the rates of the physical, chemical and
biological processes generally are slower than those in conventional
systems. On the other hand, greater time is available for the reactions
to occur at a land treatment site.
The design and operation of a land treatment facility is based on
sound scientific engineering principles as well as on field experience. A
land treatment site is designed and operated to: (a) maximize waste
degradation and immobilization; (b) minimize release of volatile organic
compounds; (c) minimize percolation of water soluble waste components; and
(d) control surface water runoff. The managerial controls at land treat-
ment sites are limited primarily to the application rates and the oppor-
tunity for cultivation (tilling), for moisture control (irrigation) and
for nutrient additions. Temperature, climate conditions, and contact
times are not control parameters.
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The land treatment of industrial wastes is receiving increasing
attention as a cost effective and environmentally sound method of waste
management. Land treatment has been used as a waste management technology
by petroleum refineries in the United States for more than 25 years. The
technology also has been used by the exploration and production sector of
the petroleum industry and for the cleanup of oil spills. About 100 land
treatment facilities exist in the U.S. petroleum industry (1). In
addition 26 of 38 Canadian refineries and at least ten refineries in
Europe use land treatment (2).
The major concerns when land treatment is used for industrial wastes
are the transformations, transport and fate of potentially toxic metals
and organics that may be in the wastes. To date, feasible waste applica-
tion rates have been based on: (a) physical and chemical characteristics
of the soil such as permeability, cation exchange capacity (CCC), and pH;
(b) mobility and plant uptake of constituents in the applied wastes; (c)
the characteristics of the waste; and (d) the degradation and immobiliza-
tion of constituents in the wastes.
Except as part of organic degradation, the soil biota rarely have
been included in any research or full scale land treatment system or
monitoring programs. However, the top layer of soil contains myriad
microbes and invertebrates that degrade and transform the applied organics
and that can affect the immobilization of the applied inorganics. To
ignore the impact of the soil biota at a land treatment site is to ignore:
(a) a major factor that may affect the performance of the site; and (b)
the impact, such as bioaccumulation of potentially toxic compounds, that
the applied wastes may have on the soil ecosystem.
The possible bioaccumulation of potentially toxic chemicals when
wastes are applied to land is a continuing concern. As identified in the
Resource Conservation and Recovery Ace (RCRA), land disposal methods are
to be protective of human health and the environment. The factors to be
taken into account in assessing such protection are the persistence, tox-
icity, mobility and propensity to bioaccumulate of hazardous wastes and
their constituents.
Earthworms are active indigenous soil invertebrates that assist the
degradation of organic compounds. In addition, in the terrestrial food
chain, earthworms represent one of the first levels of bioaccumulation
that can occur when industrial wastes are applied to the land. It is
appropriate to consider earthworms as a test organism to determine the
impact of industrial waste on soil biota when land treatment is used for
such wastes.
Microarthropods, such as mites and springtails, also are soil biota
that are found in abundance in most.soils and are secondary decomposers
and detritus feeders. Studies have shown' that they are affected adversely
by insecticides and other chemicals added to the soil.
Both earthworms and microarthropods may be useful as indicators of
the adverse effect of waste application to soil because they exhibit a
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series of effects in response to stressful situations. These are death,
decreased growth and/or reproduction, and movement away from a stressful
environment.
OBJECTIVES AND SCOPE
The overall purpose of this project was to determine: (a) the loss
and immobilization of constituents of an oily waste when the waste was
applied to the soil at different application rates, (b) the impact of the
waste and the application process on the soil biota and (c) the general
assimilative capacity of a soil when industrial wastes are land applied.
The specific objectives were to evaluate:
(a) the loss of constituents of an industrial type waste when the
waste was applied to land in the cool and humid northeast;
(b) the accumulation of waste constituents in the soil and their
bioaccumulation in earthworms when the wastes were applied at
varying rates;
(c) the impact of single, possibly large applications, rather than
continuous applications, when such wastes are land treated or
when there is an accidental application or spill of such wastes
to the soil;
(d) the effect of an industrial type waste on soil biota such as
earthworms and microarthropods.
The purpose of the project was to obtain comprehensive data that can
be used to improve the design and operating criteria for industrial waste
land treatment systems. The project was a field study with laboratory
components.
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SECTION 2
CONCLUSIONS
The objectives of this study were attained. The results indicated
that the soil has the capacity to treat wastes such as those used in this
study. Many of the organics in the applied waste were removed (lost) and
the metals were immobilized when the wastes were applied to the soil
intermittently and at varied application rates. The soil cultivation
method (rototilling) and the applied waste had an immediate adverse impact
on the soil biota (earthworms and microarthropods). However, the soil
biota did recover with time. A fraction of the applied oil and grease was
not removed during the study. The remaining organics and the metals did
not seem to have any permanent adverse effect on the soil biota.
In addition, the application of these oily wastes to the field plots:
(a) increased the pH of the acid soils (as much as one pH unit for the
higher applications), (b) increased the temperature of the soil in the
field plots that•received the higher applications by 1 to 5°C, and (c)
increased the organic matter of the soil by 1 to 5%.
The loss of organics applied to the soil varied. The loss of
specific organics (napthalenes, alkanes and certain aromatics) in the
field plots was rapid, especially in the warmer months. The half-life of
these compounds generally was less than 30 days. In comparison, the
half-life of the total oil and grease in the field plots ranged from about
260 to about 400 days. The oil and grease losses could not be correlated
to the soil temperature, to other soil parameters, to the amounts of waste
that were applied, or to the waste application rates.
All of the applied organics were not lost from the soil during the
period of the study. The separation and identification procedures used
were not able to identify the type or structure of the residual organics
that remained in the soil at the end of the study. However, based on
laboratory studies using soil from the field plots and the fact that both
earthworms and microarthropods could repopulate the soil of the plots
receiving the wastes, the organics remaining in the soil did not appear to
result in a permanent adverse impact to the soil biota.
As a result of the waste applications, the concentration of many of
the metals in the waste increased in the' top 15 cm of the plots. This
increase was especially noticeable as a result of the high and very high
applications. However analyses indicated that, except for sodium in the
very high application plots, at all of the other application rates, sodium
and the other metals were immobilized in the top 15 cm of the soil.
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The data Indicated that soil biota such as earthworms and micro-
arthropods can recover from intermittent applications of an oily waste.
With time, the numbers and kinds of soil biota in the plots to which the
wastes were applied could again become similar to those in the control
plots, although at a rate not presently predictable.
The earthworms in the field plots did bioaccumulate several metals
that were in the applied waste: cadmium, potassium, sodium and zinc.
However, when the level of bioaccumulation was compared to data from other
studies and to bioaccumulation in worms found in the control plots, it was
apparent that the land treatment of these oily wastes did not cause any
unexpected bioaccumulation of metals in the worms. The earthworms did not
bioaccumulate napthalenes, alkanes or specific aromatics that were in the
applied waste. Thus, the land treatment of these wastes did not lead to
any bioaccumulation of waste constituents that was of apparent concern.
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SECTION 3
EXPERIMENTAL PROCEDURES
GENERAL
This project was a cooperative agreement between Cornell University
and the Robert S. Kerr Environmental Research Laboratory (RSKERL) of Che
Environmental Protection Agency (EPA). The research was conducted in
laboratories of the Department of Agricultural Engineering, College of
Agriculture and Life Sciences, Cornell University, and on land adjacent to
the Cornell campus. The identification of the numbers and type of micro-
arthropods in soil samples was done by Dr. Roy A. Norton of the Department
of Environmental and Forest Biology, College of Environmental Science and
Forestry (CESF), State University of New York, Syracuse, New York.
WASTE CHARACTERISTICS
The wastes used in this study were obtained with the help of RSKERL
personnel from a site in Oklahoma on three separate occasions. The wastes
were of unknown origin but were black, viscous, and were collected from
the bottom of a lagoon that had been used to store wastes from oil refin-
eries. The characteristics of the wastes applied to the field plots on
the three dates discussed in this report are presented in Tables I and 2.
In this report, the wastes used in the study are identified as oily
wastes..
Although the wastes were collected from a large holding lagoon on
three different occasions and it was unlikely that the contents of the
lagoon were homogenous, the characteristics of the wastes were reasonably
similar (Tables 1 and 2) especially when expressed on a moisture free
basis. The water content of the three wastes did differ (Table 1).
The wastes were applied to the field plots to obtain a specific oil
content in the soil of different plots. Samples of the wastes were ana-
lyzed prior to each application date and the oil data used to determine
the volumes of a waste that were to be added to a specific plot. The
higher water content of the wastes applied in October 1982 resulted in
greater volumes of the waste being applied to achieve the desired oil
content.
The wastes contained high concentrations of several metals (Table
2). Metals such as cadmium and nickel, which can be of concern at land
treatment sites, were in low concentration.
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The oily wastes had been contained in Che holding lagoon for several
years before Che required quantities were removed and transported to Che
field siCe for application. Many volatile compounds may have been lost
during Che Cime Che wastes were held in Che lagoon.
TABLE 1. AVERAGE CHARACTERISTICS OF THE OILY WASTES APPLIED
TO THE FIELD PLOTS
Application Dace
Parameter
June
1982
October
1982
June
1983
Water, %WB
Ash, 2MFB
Oil & Grease,
g/kg MFB
ToCal Kjeldahl
Nicrogen, mg/kg MFB
Tocal Phosphorus,
mg/kg MFB
Chemical Oxygen
Demand, g/kg MFB
PH
59.0
26.9
660
2360
2620
1340
7.2
62.3
30.1
614
2320
***
ND
1250
7.1
48.7
30.2
470
2080
1760
1460
- 6.7
WB = wee basis,
**
MFB
***
moisCure free basis, ND - not determined.
Several samples of the oily waste were analyzed by RSKERL Co deter-
mine che cype of organic compounds that were in the waste. Table 3
summarizes the compounds that were identified. The identification was
accomplished by the GC/MS methods that were used at RSKERL.
PCB analyses indicated that if any of the following were present,
Arochlor 1221, 1016/1242, 1254, or 1260, the concentrations were less than
the detection limit of 0.75 micrograms/gram.
FIELD SITE
The land used for application of the' waste was an old field sice in
Tompkins County, New York, near Cornell UniversiCy. The site had noC been
used for agricultural purposes and had noC received applications of lime,
fertilizer, pesticides or herbicides for over 10 years prior to use in
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TABLE 2. AVERAGE CONCENTRATIONS OF METALS IN THE OILY WASTE
APPLIED TO THE FIELD PLOTS, mg/kg MFB*
Metal
Al
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Ti
V
Zn
June
1982
7320
73200
1.7
730
140
6100
1630
2050
110
2150
15
160
90
11
1850
Application Date
October
1982
12200
75400
2.0
780
150
8960
2660
2760
147
2880
22
206
97
18
1840
June
1983
10700
78000
1.8
770
164
9160
2240
2340
146
1670
•'" 21
253
179
17
1780
moisture free basis
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TABLE 3. ORGANIC COMPOUNDS IN THE OILY WASTE
APPLIED TO THE FIELD PLOTS*
I.
Nonane
Decane
Undecane
Dodecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Elcosane
Heneicosane
Docosane
Tricosane
Tetracosane
Pencacosane
II-
"Branched alkanes"
III.
Dime thylhexane
Dimethyloctane
Dimechylnonane
Dimethylundecane
Ethylundecane
Cyclohexylundecane
Methylpropyldodecane
Oxybisdodecane
IV.
Methylcyclopentane
Propylcyclohexane
Dimethylbenzene
Trimethylbenzene
Tetramethyl benzene
Ethylmethylbenzene
Dimethylethylbenzene
Ethenylethylbenzene
Ethylpropenylbenzene
Naphthalene
1-methylnaphthalene
2-methylnaphchalene
Dimechylnaphthalene
Methylethylnaphthalene
Trimethylechylnaphthalene
Tetrahydronaphchalene
Dihydroacenaphchalene
Isocyanatonaphchalene
VII.
Methylphenanthrene
Dimethylphenanthrene
Trimethylphenanthrene
VIII.
Dihydromethylindene
Dimechylbiphenyl
"^Determined by RSK£RL personnel using GC/MS techniques.
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this project. The site had been mowed annually to hinder growth of woody
plants.
The USDA Soil Conservation Service Soil Survey for Tompkins County
identifies the soil at the site as Rhinebeck silt loam. This soil has
about one foot of moderately to slowly permeable heavy silt loam over
slowly permeable silty clay loam or silty clay. The lower layer extends
to a depth of 2 to 3 feet and is underlain by layers of silty clay
separated by thin layers of silt. The soil is somewhat poorly drained and
exists on nearly level to moderate slopes in glacial lake areas.
The field site (Figure 1), consisted of 20 plots, 4 meters by 4
meters, with 4 meters of border area surrounding each plot. Four waste
application rates plus natural and rototilled controls were used at the
site. There were four replications for each waste application rate and
type of control. All plots were mowed prior to each waste application.
All plots, except the natural controls, were rototilled after each appli-
cation of the waste. The four rototilled control plots had no waste
applied but were rototilled. The four natural control plots had no roto-
tilling or oily waste applied and were used to separate the effects of the
rototilling and the waste applications. The applied wastes were distri-
buted over the plot surface as uniformly as possible, and were then roto-
tilled into the soil to a depth of about six inches (15 cm). Thus the
zone of incorporation for these plots was the top six inches.
Each test plot (16 m^) was marked with corner stakes to permit place-
ment of a framed grid to define 400-0.04 m2 (20 cm x 20 cm) sampling
subplots (Figure 2). Three different subplots were sampled on each sampl-
ing date to determine changes in incorporation zone characteristics and in
earthworm and microarthropod populations. To eliminate edge effects, the
edge subplots were not sampled. The subplots that were sampled from among
the 324 possibilities were determined using a random number table. Thus
different sampling locations were used at each plot each time samples were
taken. No subplot was sampled twice during the study. Examples of the
subplots that were sampled on the noted sampling days are included in
Figure 2. An elevated plank platform was used to obtain the samples so
chat the plots were not disturbed or contaminated while the samples were
taken. The project personnel did not walk on the plots except during the
waste application and the rototilling.
Natural vegetation such as grass was allowed to become re-established
on the plots in the months after the waste application.
ANALYTICAL PROCEDURES
Soil samples were taken from each plot at approximately monthly
intervals except during the winter months. Core samples were taken from
the top 15 cm (six inches) of the plots. This depth represented the depth
to which the wastes were added and mixed. At each sampling, three soil
cores were taken from the randomly determined subplots. Hand sorting was
used to determine earthworm numbers and biomass from each core. Prior to
10
-------
1«
NATURAL
CONTROL
0.4 m —
-»-« m-»
2 •
Hl'GH
3<
CONTROL
4 *
MEDIUM
V
5 A
LOW
ERY HIGH
6A
LOW
7«
NATURAL
CONTROL
BB
HIGH
9 <
CONTROL
10*
MEDIUM
VERY HIGH
1 1 *
MEDIUM
12 A
LOW
13*
NATURAL
CONTROL
14B
HIGH
1 SI
CONTROL
VERY HIGH
16«
CONTROL
1 7 *
MEDIUM
18 A
LOW
19 •
NATURAL
CONTROL
201
HIGH
VERY HIGH
'CHANGED JUNE 1983| SEE TABLE 7 FOR ACTUAL APPLICATION RATES
FIGURE 1
SCHEMATIC OP THE PLOTS USED IN THE FIELD STUDY
-------
EXAMPLE OF SUBPLOTS SAMPLED ON SPECIFIC SAMPLING DATES
UfCftO •
ARTHAOPO OS
C ABTMWOHMS
A PRI L -4
F-17
H-1S
C-11
S-9
P-6
L-3
M A Y- 5
E-14
B-17
J-10
K-13
K-2'
F-5
JU NE -6
R-17
Q-14
P-13
K-8
R-5
0-4
JU L Y -7
E-16
H-18
P-8
O-12
G-4
F- 7
10
too
ABCOEFGHI JKLMNOPORST
-INDICATES EDGE PLOTS NOT TO BE SAMPLED
FIGURE-2
SUBPLOTS IN EACH TEST PLOT USED FOR SAMPLING
12
-------
measuring Che physical and chemical characteristics of the soil, the cores
from each plot were composited. Residual soil was returned to the plots
and used to fill in the core holes.
The microarthropod samples were soil cores approximately 6 cm in
diameter and 6 cm deep. The microarthropods were separated from the soil
by inverting the soil core in a heat-gradient extractor for one week. The
upper half of the soil core was heated by light bulbs and the lower half
exposed to the ambient temperature in a 5°C environmental chamber. The
microarthropods followed the humidity gradient that was established and
fell from the bottom of the funnel into collecting jars of ethanol preser-
vative. The type of microarthropods were identified and counted. Greater
details about the microarthropod extraction and identification procedures
are presented in Appendix A.
Metals and certain organics in the waste, soil and earthworm
samples were analyzed by personnel at the EPA Robert S. Kerr Environmental
Research Laboratory (RSKERL). Cornell personnel analyzed the waste and
soil samples for more routine parameters. Dr. Norton (CESF) counted and
identified the microarthropods.
The analyses conducted by RSKERL and Cornell personnel are noted in
Table 4. The methods used to analyze the waste and soil samples at
Cornell are noted in Table 5. In addition, Cornell personnel counted and
identified the earthworms.
Soil, waste, and earthworm samples were analyzed for metals and
specific organics at RSKERL. Dried samples of the soil and earthworms and
liquid samples of the waste were sent to RSKERL for metal analysis. For
organic compounds, methylene chloride extracts of the soil and earthworms
were sent to RSKERL for analysis. The extracts were prepared by mixing 10
grams of wet sample with anhydrous sodium sulfate and extracting the
mixture for two hours or at least 20 cycles with methylene chloride. This
extraction method was supplied to the Cornell investigators by the RSKERL
project officer. The methods used to prepare the soil and worm samples
for analysis by RSKERL are presented in detail in Appendix B.
The impact of the waste on earthworms was evaluated in the laboratory
using the general methodology outlined in Figure 3. The contact and arti-
ficial soil tests were developed and tentatively approved by the European
Economic Community (EEC) (7). The growth and reproduction tests have been
developed by Cornell personnel, have been evaluated with many chemicals
and wastes, and have been used in other research studies. With each of
the earthworm tests, controls were Included. The details of these methods
are presented in SECTION 4.
A quality assurance plan was prepared by the Cornell investigators
and approved by the RSKERL project officer in early 1982. That plan
identified sampling procedures, quality control checks, and procedures to
assess data precision and accuracy.
13
-------
TABLE 4. FIELD STUDY MEASUREMENTS
Parameters
Samples Measured
I. Oily Waste total solids
volatile solids
COD
TKN
total phosphorus
pH
oil
metals
specific organics
II. Earthworms metals
specific organics
III. Field Test metals
Plot Soils specific organics
CEC
total solids
volatile solids
pH
TKN
oil and grease
Laboratory That
Performed Analysis
Cornell
Cornell
Cornell
Cornell
Cornell
Cornell
Cornell
RSKERL
RSKERL
RSKERL
RSKERL
RSKERL
RSKERL
Cornell
Cornell
Cornell
Cornell
Cornell
Cornell
14
-------
TABLE 5. METHODS USED FOR ANALYSIS OF WASTE AND SOIL SAMPLES
Parameter
Method
Sample
Waste Soil
Moisture
(Total Solids)
Ash
Volatile Solids
Total Kjeldahl
Nitrogen (TKN)
Total Phosphorus
Chemical Oxygen
Demand
Oil and Grease
pH
Temperature
Standard test method for water in
petroleum products and bituminous
materials by distillation -
ANSI/ASTM D95-70*
Total residue dried at 103-105°C -
Standard Methodst, 209A. and Methods
of Soil Analysis§. 7-2.2.
Standard test method for ash from
petroleum products - ANSI/ASTM D482-80*
Total volatile and fixed residue -
Standard MethodsT, 209 E
Semi-micro Kjeldahl technique -
McKenzie and Wallace (1954) and
Standard Methodst, 420 B.
Sulfuric acid - nitric acid digestion -
Standard Methods, 424 C II followed by
Vanadomolybdophosphoric acid colori-
metric method - Standard Methods!, 424 D.
Bichromate reflux method, Standard
Methodst, 508 A.
Extraction method for sludge samples -
Standard MethodsT, 502 D.
Glass electrode - Standard Methodst. 423
Measurement in 0.01 M CaCl2 solution -
Methods of Soil Analysis§, 60-3.5
Bimetallic thermometer - Methods of
Soil Analysis§. 2-2.3
X
X
X
*Reference 5
tReference 3
§Reference 4
15
-------
CONTACT TEST
TWO DAYS
T
RESULTS PROVIDE A
RAPID INDICATION OF
POTENTIALLY TOXIC AMOUNTS
ARTIFICIAL SOIL TEST
TWO WEEKS
RESULTS NARROW
THE RANGE OF
CONCENTRATIONS THAT
MAY BE INHIBITORY
GROWTH AND REPRODUCTION STUDIES
EIGHT WEEKS
RESULTS IDENTIFY THE
RANGE OF CONCENTRATIONS THAT MAY
HAVE AN IMPACT IN FIELD STUDIES
FIGURE 3
METHODOLOGY USED TO DETERMINE THE
IMPACT OF WASTES ON EARTHWORMS IN THE LABORATORY STUDIES
16
-------
In addition, samples of a freeze-dried, digested municipal sludge
standard were supplied from EPA-Cincinnati through the RSKERL project
officer to Cornell. Such samples were used to determine the precision of
the analyses being run at Cornell (Table 4). The analyses for all
parameters were very close to the mean values identified by EPA for the
standard sludge sample. Samples of the "standard" sludge were analyzed
periodically as part of the routine monthly sampling and analysis.
Results of these quality assurance analyses for oil and grease are
presented in Appendix K.
At Cornell, for each waste sample and each parameter, at least five
replicates were analyzed and used to determine a mean and standard devia-
tion. For each soil sample and each parameter, at least two replicates
were analyzed.
SPECIAL STUDIES
Two special studies were conducted to determine: (a) the variability
in the characteristics of Che soil samples taken from various locations in
the field plots, and (b) the precision and accuracy of the analytical
method used for oil and grease when used with soil samples. The spatial
variability study identified the extent to which the variability of the
data was due to the non-homogeneity of waste application and rototilling.
The results of the oil and grease analytical method evaluation established
the extent to which this method extracted the oil and grease in the waste
and soil samples. These special studies and the results that were
obtained are presented in Appendix C (spatial variability) and Appendix D
(oil and grease analytical method).
17
-------
SECTION 4
LABORATORY STUDIES
The laboratory studies determined the tolerance level of earthworms
to the waste. The worms were Eisenia fetida, a worm used extensively in
laboratory studies throughout the world. The three step program noted in
Figure 3 provided an indication of the waste concentrations that had an
impact on the worms.
The contact test method generally is the first method used for these
purposes. The contact test attempts to determine the approximate lethal
concentration for the waste being tested. A filter paper strip is
inserted into a small (4 oz.) glass vial to cover the sides of the vial
and a specified amount of a waste or chemical is evenly distributed over
the filter paper. Due to the viscous nature of the oily waste, it was
difficult to utilize small uniform samples in the contact test. Because
of these problems, the results of the contact test were inconclusive.
The artificial soil test is used to quantify the toxic effect of the
specific waste or chemical being tested. Because soils are a heterogenous
mixture, an artificial soil containing, on a dry wet basis, a mixture of
sand (69%), kaolinite clay (20%), ground peat (10%) and limestone (1%) is
used in this test. The pH of the mixture is adjusted to 7.0 using the
limestone, and the moisture content is adjusted to 35% using deionized
water. The test containers are covered 125 mm x 65 mm dishes with 400 g
(dry weight), of the test medium. There were four replicates for each
waste concentration tested. Ten adult worms were used per test. The
average weight of the worms was determined at the beginning and end of
each test, which ran for 14 days. Worm survival also was recorded. The
results are discussed later in this section.
Neither the contact or artificial soil test indicates the sublethal
effects that a particular chemical might have on earthworm growth rates or
reproduction. The growth and reproduction test is used to evaluate such
effects.
In the growth and reproduction test, a specific quantity of waste was
mixed with horse manure, a known earthworm food source. The resultant
waste concentration was based on the oven dry weight of the food source.
The mixture was placed on a layer of moistened soil in a 20 mm x 100 mm
petri dish. Two E_. fetida, less than 10 mg each, were added to each
dish. Four replicates of each waste concentration were included. Four
and six weeks after the experiment was initiated, the residual mixture was
removed from the dishes and the worms were fed a fresh mixture that
18
-------
included Che proper waste concentration. The worms were weighed at four,
six, and eight weeks. These weights as well as the cocoon production,
were compared to controls to determine the sublethal effects of the waste
being tested. Results of these tests also are discussed later in this
section.
These studies determined the impact of the wastes on the earthworm
E. fetida under controlled laboratory conditions. The intent was to
obtain an estimate of the impact: (a) before the liquid waste was applied
and therefore to obtain some estimate of the application rate that should
be used initially; and (b) so that the impact could be compared to data
that would result from the field studies.
Neither the artificial soil or the growth and reproduction tests are
identical to conditions that occur in a field land treatment site. In
both tests, there is little opportunity for loss of volatile constitu-
ents. In addition the microorganisms in the media may not be acclimated
to the waste and degradation may not be as rapid as it would be In the
field. Worms other than _E. fetida may exist at a field site. The media
used in the artificial soil test approximates the conditions in a field
soil reasonably well. However, the media used in the growth and reproduc-
tion test contain more organic matter and a greater cation exchange
capacity (CEC) than exists in field soils. In spice of these differences,
the results obtained using these tests can identify the relative impact of
a waste when it is applied to the soil.
The results of the artificial soil test indicated that the oily waste
can affect the survival of E. fetida (Figure 4). This impact was observed
when the concentration of waste to which the worms were exposed exceeded
about 1000 rag wet waste per kg of artificial soil (wet weight). This
corresponded to about 420 mg of oil and grease per kg of artificial soil
on a moisture free basis. The LC50 value was determined using the mehtod
of Litchfield and Wilcoxon (40) and was 1540 mg of the wet waste per kg of
the artificial soil. The 95% confidence interval values were 1360 and
1670 mg/kg.
Results obtained in the growth and reproduction tests are shown in
Figure 5. At waste concentrations up to 20,000 mg wet waste per kg dry
weight of horse manure, no decrease in worm weight occurred (Figure 5).
Cocoon production per worm (Figure 5) and cocoon viability did not
decrease until large quantities of the waste were incorporated in the
manure.
The impact of the higher concentrations of the oily waste was abrupt
and severe. At concentrations of 25,000 mg wet waste per kg dry weight of
manure or greater, all the test worms died. For this waste, the concen-
tration of 20,000 mg wet waste/kg dry manure was the equivalent of an oil
concentration of about 5400 mg/kg dry manure or about 0.54% by weight.
The results of the growth and reproduction test were different
(showed less impact) than those of the artificial soil test (Figure 4)
with respect to worm mortality. The different characteristics of the
19
-------
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artlllclal toil, 39 °/e moi 1 1 ur •
4O9 940 870
kg artificial toll, 3 9 °/o moi t lura
030 840 1.090
/ kg artificial toll, moltlur* free
W&STE CONCENTRATION IN TEST MEDIUM
FIGURE 4
TOXIC1TY OF 'HIE OILY WASTE IN THE ARTIFICIAL SOIL TEST
-------
GROWTH AND REPRODUCTION TEST
u
X
ec
o
i
01 400
S
« r
u ui
e
u
2OO
O
O
(mg
(mg
(mg
5,000 1O.OOO I5.OOO 20,OOO 25.0OO
wet waste /kg dry weight of test medium)
2.O5O 4,1OO 6,150 8.2OO 1O.2SO
dry waste kg dry weight of lest medium)
1.36O 2.72O 4.O80 5.44O 6,8 OO
oil & grease / kg dry weight of test medium)
WASTE CONCENTRATION
IN TEST MEDIUM
FIGURE 5
WORM BIOMASS AND COCOON PRODUCTION IN THE
GROWTH AND REPRODUCTION TESTS
21
-------
media in the two tests was one reason for the different results. The
artificial soil test medium consists of sand, peat, kaolin and a small
amount of limestone plus the waste. Microorganisms that may aid in
decomposition of organics are only added with the wastes.
The growth and reproductive test medium is a mixture of horse manure
and the waste source. This media is much higher in organic content and in
indigenous microorganisms than the artificial soil test media. The
greater organic content provides more sorption sites for components of the
waste and the microorganisms can increase the decomposition of the
organics in the wastes. Both factors could decrease the toxicity of the
waste to the earthworms.
The artificial soil test method also was used with soil from several
of the field plots to determine whether the waste-soil mixture had an
adverse effect on the worms. In these experiments, soil from the zone of
incorporation at the plots replaced the artificial soil. The results are
presented in Table 6. For the medium and high plots (plots 11 and 14),
the most recent waste application had been in October 1982. Thus the
results show the effect of the residual waste after a nine to eighteen
month period. For the very high plots, the most recent application had
been in June 1983 and was the highest application rate used.
The worm survival data from Table 6 were compared (Figure 6) to the
interval of time between when the waste was applied to the plot and when
the soil samples were taken for these artificial soil analyses. Although
the soils were taken from different plots and different waste applications
had occurred, a general pattern is apparent. Greater worm survival
resulted when there had been a longer interval of time since the waste had
been applied.
Considerable loss of oil and grease occurred after the waste applica-
tions (SECTION 5). The lower molecular weight and more easily biodegrad-
able organics were lost more rapidly. Therefore organic compound concen-
trations different from those in raw wastes were present in the soils used
in these artificial soil tests. The total oil and grease content of the
soils thac were used in these cescs are presented in Taole 6.
Several inferences are apparent from the data in Table 6. First, the
apparent adverse impact when using the field soils occurred at higher oil
and grease concentrations than the impact that resulted from the oily
waste in the previous artificial soil and growth and reproduction tests
(Figures 4 and 5). However, it should be recognized that the oil and
grease test is only a gross measure of the waste constituents in a soil or
a waste and that biodegradation and volatilization had occurred in the
field soils.
The second inference is that even nine to eighteen months after the
October 1982 waste application, some residual adverse impact to the worms
could be discerned (Figure 6). Third, there was an immediate adverse
effect on the worms from the June 1983 very high application and all of
the worms died. Four months later (October 1983), there was a less severe
22
-------
TABLE 6. RESULTS OF THK ARTIFICIAL SOIL TEST USING SOI I, OBTAINED FKOM SPECIFIC FIELD PLOTS
ON THE NOTED SAMPLING DATES
N9
LJ
Percent of Initial Worm Weight*
Plot
Number
13
11
14
5
6
12
18
Plot
Type
Natural Control
Medium
High*
Very High™
Very High
Very High™
Very High
July
1983
101
87
65
0+
0
0
0
October
1983
109
92
77
53
59
65
60
April
1984
102
98
89
75
81
68
72
Oil and Grease in the Noted Plots**
July
1983
650
5,100
16,340
47,600
59,200
54,000
62,600
October
1983
540
5,720
11,460
32,700
35,100
34,000
35,000
April
1984
570
4,990
10,500
27,900
29,100
34,000
35,600
*The weight of the worms after 14 days as a percentage of the weight of the worms at the beginning of the
experiments.
**Average mg of oil and grease per kilogram of soil (MFB) in the soil from the plots that were used in the
artificial soil test.
A value of zero indicates that all the worms died.
tt
Previous waste application occurred in October 1982.
Previous waste application occurred in June 1983.
-------
1OO
"o
£ 80
o
o
o
60
Z
O 4O
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20
MEDIUM PLOTS
HIGH PLOTS
/
VERY HIGH PLOTS
Artificial Soil Test
impact of incorporated
waste on worm growth
0 4 8 12 16 2O
MONTHS AFTER WASTE APPLICATION
FIGURE 6
THE IMPACT OF SOIL FROM THE FIELD PLOTS ON EARTHWORM SURVIVAL USING
THE ARTIFICIAL SOIL TEST
24
-------
impact and even less of an impact ten months later (April 1984). The
applied waste became less toxic to the worms with time, again probably due
to the degradation and loss of components of the applied oily waste.
As is discussed in SECTION 5, there were many factors that affected
the number and biomass of worms in the field plots—temperature, moisture
content, rototilling, vegetation or lack of it, and the applied waste.
The artificial soil test data in Table 6 does identify the immediate and
lingering impact of the applied waste and adds to the understanding of how
the changes that took place in the field plots affected the earthworms.
The results from the artificial soil tests using the field soils
demonstrate that: (a) oily wastes of the nature used in this study can
adversely affect the earthworms in the soil, and (b) as the organic
compounds are lost from the soil, the adverse impact is decreased. These
results were verified by data on earthworm numbers and biomass obtained
from the plots during the study (SECTION 5).
25
-------
SECTION 5
FIELD STUDY
WASTE APPLICATION
The oily waste was applied to specific test plots in June 1982,
October 1982, and June 1983. These were the times when the wastes were
able to be obtained from Oklahoma. The characteristics of the wastes
applied on these dates have been presented in Tables 1, 2 and 3. The
field plots were identified in Figure 1.
In October 1982, the low, medium and high plots received larger
application rates than were applied in June 1982. In June 1983, a very
high waste application was made to field plots 5, 6, 12 and 18, the plots
that had received the initial Low application rates. Thus the effect of
seven application rates, ranging from 0.17 to 9.5 kg oil per meter of
surface area was evaluated. The application rates for the respective
plots are noted in Table 7. The rates spanned the range likely to be used
under actual field conditions.
Only the indigenous nutrients and trace elements in the soil and the
waste were available to the micro- and macroorganisms as the wastes were
degraded. No fertilizers or other amendments were added to the plots.
The plots were only cultivated (rototilled) immediately before and
after the wastes were applied. No subsequent cultivation occurred to
aerate the zone of incorporation. The plots were undisturbed after the
combined waste applications and rototilling and only natural aeration
occurred in the plots. This is different ^han what would occur at most
industry land treatment sites where frequent tilling may occur to promote
mixing and aeration and to increase degradation and other losses. This
approach was taken in order to approximate the changes that would occur
under conservative and non-optimum conditions such as when there may be
single or highly intermittent waste applications or when a spill would
occur. The approach also caused one less variable, the frequency and type
of aeration (tilling), to be included in the study.
CLIMATIC DATA
Suitable environmental conditions, especially temperature and mois-
ture content, are necessary for the soil biota and for degradation of the
organic matter in the applied waste. The precipitation and soil tempera-
ture patterns that occurred at the field site are shown in Figures 7 and
26
-------
TABLE 7. FLELD PLOT STUDY APPLICATION RATES, kg/in2
ro
Plot
Number
5
6
12
18
4
10
11
17
2
3
14
20
Wet
Waste+
0.63
0.63
0.63
0.63
1.25
1.25
1.25
1.25
2.49
2.49
2.49
"2.49
June 1982
Dry
Matter-H-
0.26
0.26
0.26
0.26
0.51
0.51
0.51
0.51
1.02
1.02
1.02
1.02
October 1982
Oil &
Grease
0.17
0.17
0.17
0.17
0.34
0.34
0.34
0.34
0.68
0.68
0.68
0.68
Wet
Waste
4.94
4.94
4.94
4.94
9.94
10.90
9.94
9.94
19.80
19.80
19.80
19.80
Dry
Matter
2.09
2.09
2.09
2.19
4.20
4.60
3.98
3.98
7.76
6.71
6.91
6.08
Oil &
Grease
1.41
1.41
1.41
1.62
2.83
3.10
2.52
2.52
4.46
5.31
4.74
3.72
June 1983
Wet
Waste
39.7
39.7
39.7
39.7
NA*
NA
NA
NA
NA
NA
NA
NA
Dry
Matter
20.4
20.4
20.4
20.4
NA*
NA
NA
NA
NA
NA
NA
NA
Oil &
Grease
9.5
9.5
9.5
9.5
NA*
NA
NA
NA
NA
NA
NA
NA
*No application - waste only applied to plots 5, 6, 12, and 18 in June 1983.
+The quantities of wet waste applied were determined by weighing. A barrel of waste was weighed, the waste
pumped out and applied, the weight of the barrel and any residue determined, and the amount applied to a
plot determined by difference. Although every attempt was made to have each barrel applied on a given day
contain the same material, it was not always possible. Some of the barrels contained different amounts of
water and oil and grease. The data in this Table indicate Lhe amounts that were added to the noted plots.
++Dry matter was determined by subs tract ing the moisture content of the waste, measured using the method in
Table 5, from the wet weight of the waste.
-------
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200
180
160
140
120
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80
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MEAN PRECIPITATION
. 1958 - 1078 I
1983
FIGURE 7
MONTIIIY PRECIPITATION AT THE FIELD SITE
-------
SOIL TEMP. (15 cm depth)
AIR TEMP. (130 cm height)
to
vO
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e
Ul
K
D
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25
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15
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FIGURE 8
MONTHLY AVERAGE SOIL AND AIR TEMPERATURES AT ITHACA, NY
-------
8. The summers of 1982 and 1983 were relatively dry as shown by the pre-
cipitation data (Figure 7). The winters of 1982-83 and 1983-84 were rela-
tively mild and the upper 15 cm of the soil was frozen for only a short
period of time during these winters. The average soil temperatures at a
depth of 15 cm consistently were warmer than the average air temperature
(Figure 8).
The data in Figure 8 represent average monthly data for an official
weather station less than one-half mile from the field site. The soil
temperatures measured at the 15 cm depth in the control field plots
throughout the year were within 1 or 2°C of the soil temperatures at the
official weather station. Thus, the soil temperature pattern noted in
Figure 8 can be considered as representative of the pattern at the field
site.
Because of wet and cold conditions during the latter months in 1983
and the spring of 1984, no soil samples were taken from the plots during
the periods of December 1982 through February 1983 and November 1983
through April 1984.
SOIL CHARACTERISTICS
General - Some of the soil characteristics changed as a result of the
waste application. Figures 9 and 10 indicate typical results. For
clarity, only the average values for the natural control, high and very
high plots are presented. Also shown are dates when the waste was applied
and when the soil samples were taken. The mean values for the character-
istics of the plots receiving similar application rates are noted in
Appendix F.
pH - The pH of the plots that received the high applications of the
oil waste increased. The increase was pronounced for the plots that
received the very high applications in June 1983 (Figure 10). With the
very high application, the soil pH increased by more than one pH unit.
After the waste applications, the pH stayed at above background levels
during ihe rast of the study (Figures 9 and 10).
Nitrogen and Volatile Matter - There were no statistically signifi-
cant increases in the nitrogen content of the soils (Figure 9) as a result
of the waste applications. The TKN concentration in all of the plots was
about 3.5 grams per kilogram of moisture free soil.
The volatile matter in the soil was increased by the waste applica-
tions (Figure 9). Until the waste applications in October 1982, the
volatile matter in the plots was about 9% of the soil on a moisture free
basis. After the October 1982 application, the volatile matter in the
medium application plots was about 10% and in the high application plots
was about 11%. After the application in June 1983, the volatile matter in
the very high application plots was in the range of 14 to 15%. There
appeared to be a slight decrease of the volatile matter in the very high
application plots with time.
30
-------
WASTE
APPLICATION
VERY HIGH
HIGH
NATURAL CONTROL
X
a
6.0
5.5
30
VERY HIGH WASTE APPLICATION
I 1 i
I 1 1 _ . J
JJASONOJFMAMJJASONOJFMAMJJ
19U2 • 1B83 ' ' 1984——
* V. moltlure lr«« toll
•*mg/g monlura Ira* toll
FIGURE 9
MEAN VALUE OF pH, VOLATILE MATTER AND TKN IN THE SOIL OF TIIE FIELD PLOTS, n
-------
8.0
7.0
Z
a
O 6.0
5.0
VERY HIGH
WASTE
APPLICATION
LOW /VERY HIGH
NATURAL CONTROL
MAMJ JASONDJ FMAMJJ
1983 *—• 1984 *
FIGURE 10
EFFECT OF THE JUNE 1983 VERY HIGH WASTE APPLICATION ON THE MEAN VALUE OF SOIL pll, n =
-------
Oil and Grease - The oil and grease in the top 15 cm of soil
increased as a result, of the waste applications (Figure 11). It was not
possible to sample the plots immediately after the waste applications. To
indicate the loss patterns that occurred, the oil and grease concentra-
tions that should have been in the soil immediately after the June and
October 1982 applications were calculated and portrayed on Figure 11. The
ranges that occurred in the respective plots are shown in Figure 12 for
the very high application rate plots and in Figure 13 for high application
rate plots. The range of concentrations were influenced by the spatial
variation factors discussed in Appendix C.
With time, the concentration of oil and grease in the soil
decreased. However, the applied oil and grease was not lost completely.
After each waste application, a new apparent background concentration in
the respective plots resulted.
In reviewing the oil and grease losses and accumulations that occur-
red, it should be recognized that the oily waste came from the bottom of a
holding lagoon in Oklahoma. The source of the wastes stored in the lagoon
is unknown but probably was from nearby refineries. Typical refinery
wastes disposed of in the lagoon may have included oil-water separator
sludges, oily tank bottoms, dissolved air flotation (DAF) sludges, and
other residual oily materials. While the wastes were stored In the
lagoon, some of the volatile compounds may have been lost. Thus the oily
wastes applied to the field plots were not necessarily typical of refinery
wastes.
The background oil and grease concentration in the soil of the
control plots was about 0.4 g oil and grease per gram of moisture free
soil. This is comparable to the background data reported for soils at
Marcus Hook, Pennsylvania; Tulsa, Oklahoma; and Corpus Christi, Texas
(12).
The oil and grease loss pattern had the appearance of a first order
type reaction (Figures 11, 12 and 13). The data was analyzed to see if a
first order type equation represented the data and if the oil loss could
be related to temperature. The resultant correlations, Loss rates and
calculated half life values are presented in Table 8. Data from the first
applications in June 1982 were not used due to the low amounts that were
applied and small losses that occurred. The mean values for the
respective plots are presented in Appendix F.
As indicated from the correlation coefficients (Table 8), a first
order equation was a reasonable assumption for the data. The total oil
and grease loss rate constants were essentially the same for the medium,
high and very high waste application plots. The loss rate constant for
the low waste application plots was' higher. The reason for this higher
loss rate constant is unknown. It was not related to the type of oil
waste applied or to the concentration of oil and grease in the soil. The
same waste was applied to all three series of plots (low, medium and high)
at the same time (October 1982). The latter plots (medium and high) had
33
-------
Ill -
5s
III 3
« E
rl 01
o •*
30
25
20
15
10
WASTE
APPLICATION
HIGH
MEDIUM
LOW
NATURAL CONTROL
VERY HIGH WASTE APPLICATION
f . f • . : : : . f . :—•
JJASONDJFMAMJ JASONDJFMAMJJ
• 1982 *• - 1983 •• 1984 ••
FIGURE 11
AVERAGE OIL AND GREASE CONCENTRATIONS IN THE SOIL OF THE FIELD PLOTS
-------
60
40
• It
U >•
::
u >-
a a
0 •
20
10
AVERAGE -
STANDARD
[- DEVIATION
VERY HIGH APPLICATION RATE
WASTE
APPLICATION
JJASONOJFMAMJJ
1 19 U 3 •• •• 1084 -"
F1CURE 12
AVERAGE OIL AND CREASE CONCENTRATIONS IN THE SOIL OF THE VERY HIGH
APPLICATION FIELD PLOTS
-------
o
M
ft)
0)
30
25
2O
O
3
M
'5
E
n 15
3 10
Ul
oc
0
WASTE
APPLICATION
Avnurt sDTEr>*55
HIGH APPLICATION RATE
AVERAGE OIL AND
ONDJFMAMJJASONDJ FMAMJJ
-1982-*- -• 1983 »~ -« 1984 +•
F]GURE 13
GREASE CONCENTRATIONS IN THE SOIL OF THE HIGH APPLICATION FIELD PLOTS
-------
TABLE 8. TOTAL OIL AND GREASE LOSS IN THE FIELD PLOTS
Period
of Loss
10/82 to 6/83
(223 days)
10/82 to 7/84
(612 days)
10/82 to 7/84
(612 days)
6/83 to 7/84
(390 days)
*The loss rate
Plots
Low
Application
Medium
Application
High
Application
Very High
Application
from a first order
Loss Rate*
Constant
(K)
(days'1)
0.0026
0.0016
0.0018
0.0017
equation,
Correlation
Coefficient
(R2)**
0.83
0.88
0.88
0.83
i.e. Ot = 00e~Kt
Half -Life
(t1/2)(days)
267
433
385
408
where
Ot = total oil and grease concentration in the soil (gram/kg soil
MFB) at time t (days), 0Q = total oil and grease concentration in the
soil at time
constant
(day-1).
zero (t0), and K = total oil and grease loss rate
**Correlation coefficient for the first order equation.
37
-------
higher initial oil and grease concentrations in the soil but had the same
loss rate constants.
The loss rates resulted in long half lives (tj/2) for the total oil
and grease in the respective plots. For the low application plots, the
half life was about 300 days while for the medium, high and very high
application plots, the half life was about 400 days (Table 8).
It was not possible to statistically correlate the oil and grease
losses to the soil temperatures in the field plots. Intuitively, tempera-
ture should have an effect on such losses since temperature affects the
rates of biodegradation and of volatilization, the most likely mechanisms
of loss in the field plots. However, any effect due to temperature could
not be discerned and separated from other parameters affecting the oil
losses. The effect of temperature probably was masked by factors such as
the variability in the oil and grease data, differences in soil moisture
as the soil temperature changed, and the different oil and grease
compounds that were present in the soil at different times during the
study. The oil and grease loss patterns (Figures 11, 12 and 13) do
indicate greater losses during the warmer periods of a year and less loss
during the colder periods.
Although a first order equation apparently was a reasonable mathema-
tical expression to portray the oil and grease losses, realistically It is
not completely acceptable since first order equations of the type shown in
Table 8 indicate that eventually there will be a complete loss. The data,
however, suggests otherwise. Some of the applied oil and grease appeared
to remain in the soil even after twelve or more months.
The oil and grease losses had not completely ceased by the last
sampling date in July 1984. The available data was analyzed to determine
the maximum amount of loss that would occur and, by difference, to deter-
mine the "biodegradable" fraction of the applied waste. The results are
presented in Table 9. There is the possibility that the waste applied in
June 1983 was less degradable than the waste applied in October 1982 even
though: (a) the general characteristics of the applied wastes (Table 1)
were not drastically different on a moisture free basis, and (b) and the
total oil and grease loss rates for the different wastes were essentially
the same (Table 8).
The constituents of the refractory fraction of the wastes were not
determined. It is postulated that they are long chain, high molecular
weight oily compounds such as asphaltenes, paraffins and similar
compounds.
Even though there was an apparent large accumulation of oil and
grease that resulted from the very 'high application in June 1983, these
ultimate residuals may not have any adverse environmental impact. As was
noted earlier (SECTION 4), soil from the very high plots was used in the
artificial soil test to determine' the impact of the residuals to earth-
worms. The results of these tests (Table 6) indicated that any adverse
impact decreased with time. As the artificial soil test results note, the
38
-------
TABLE 9. MAXIMUM ESTIMATED OIL AND GREASE LOSS IN THE FIELD PLOTS
Maximum Estimated Refractory
Plots Loss* Fraction**
Waste Applied October 1982
Low Application 78% 22%
Medium Application 76% 24%
High Application 80% 20%
Waste Applied June 1983
Very High Application 52%+ 48%
*The loss that would occur over a period of time longer than that of the
study. This loss is equivalent to the fraction of the applied waste
that is able to be lost by biodegradation, volatilization or other
mechanisms.
**The fraction of applied material estimated to remain in the soil from
the noted application.
+The maximum predicted loss for the very high application was obtained
using data collected over 390 days whereas the maximum predicted losses
for the low, medium and high applications were obtained using data
collected over 612 days. When data collected over the first 350 days
after the waste was applied was used to estimate the maximum loss, the
maximum predicted loss for the low, medium, and high application plots
was about 40% whereas for the very high application plots, it was 52%.
It is possible that a smaller refractory fraction would have
estimated from the very high application data had there been time to
collect more loss data over a longer time period (such as over 600
days).
39
-------
residuals from the medium and high applications of October 1982 had prac-
tically no effect on the earthworms. The inference that the refractory
residuals may not have an adverse impact also is verified by data on
earthworm numbers and biomass discussed later in this SECTION.
Temperature - The soil temperature in the field plots are portrayed
in Figure 14. The temperatures of the plots receiving the oily waste did
not increase after the first waste application in June 1982. Because of
the cold weather after the October 1983 waste application, there also was
no difference in soil temperature of all the plots until the summer of
1983. During that summer, the soil temperature of the plots receiving
the high waste application was greater than that of the other plots by 1
to 1.5°C. During the period of June 1982 through May 1983, the tempera-
ture variation among the means for the different plots was less than 1°C.
The temperatures of the high application rate plots were no different than
that of the natural control plots by the fall of 1983.
After the very high waste application was made to plots 5, 6, 12 and
18 in June 1983, the soil temperature of these plots was noticeably
higher than that of the other plots (Figure 14). The temperature of the
incorporation zone of the very high plots was from 3 to 5°C greater than
that of the natural controls. The temperature increase may be due to the
absence of surface vegetation and the darker color of the surface soil.
Although the temperatures in the very high plots decreased to chat of
the natural controls by November 1983, the increase again occurred during
the spring and summer of 1984 (Figure 15). During this period, no tilling
occurred, no vegetation grew on the very high plots and the color of the
soil continued to be darker than that of the other plots.
Soil Moisture - The moisture content of the top 15 cm of the soil in
the field plots changed throughout the project (Figure 16), decreasing
during the summer months. Generally the soil moisture ranged from 20 to
32% on a wet basis.
The soil moisture pattern was the reverse of that of soil temperature
(Figure 8) which increased during the summer mouths. Both »oil moisture
and soil temperature will have an effect on the soil biota.
Cation Exchange Capacity - The cation exchange capacity (CEC) of the
soils in the field plots was analyzed periodically throughout the
project. The purpose of the analyses was to ascertain whether the appli-
cation of the oily waste had any effect on the CEC of the soil. There
were some variations between the plots but no trend with time or with the
waste application rate was identified. The average CEC values for the
specific types of plots are noted in Table 10. The detailed CEC data are
summarized in Appendix E.
Metals - The average metal concentrations in the soil at the field
plots are summarized in Appendix G. Although there were high concentra-
tions of certain metals in the wastes (Table 2), the application of the
40
-------
,° JO
u
3
4
-------
30
25
20
U
o
U
K 15
3
10
x
to
5
O
VERY HIGH
WASTE
APPLICATION
VERY HIGH
NATURAL CONTROL
J J A S O N D
1083
J F M A M J J
1984 -
FIGURE 15
SOIL TEMPERATURES IN THE NATURAL CONTROL AND VERY HIGH APPLICATION PLOTS - 1983 - 1984
-------
10
27
. 2*
kl
OC
3
H
ff 18
5
1
is
o
12
• NATURAL CONTROL
• ROTOTILLCD CONTROL
A LOW
• MEDIUM
• HIGH «
* VERV HIGH
JJASONOJFMAMJJASONDJFMAMJJ
1982 t983 1984 .
FIGURE 16
AVERAGE SOU. MOISTURE IN THE FIELO PLOTS - 1982 - 1984
-------
wastes did not always result in measurable increases in metal concentra-
tions in the soil. This was particularly true for the applications in
June 1982 and for some of the applications in October 1983.
TABLE 10. AVERAGE CEC VALUES FOR THE SOILS AT THE FIELD SITE
Type of CEC Values
Application (meq/100 gram)
Natural Control 24.8 ±4.6
Rototilled Control 26.0 ± 5.8
Low 25.5 ± 3.8
Medium 24.5 ± 3.2
High 25.9 ± 5.0
Very High 24.0 ± 4.4
*Average and standard deviation.
Mass balance estimates were made to identify the increase in soil
metal concentrations that should have occurred as a result of the seven
waste applications. This was done by calculating: (a) the metal concen-
tration in the top 15 cm of the soil before an application, and (b) the
metal concentration in the top 15 cm that should have resulted after the
waste was applied and rototilled into the top 15 cm. These independent
calculations were done to ascertain whether the waste applications should
have resulted in a measurable increase in the soil metal concentrations.
Such calculations also avoided any differences that may have been caused
by incomplete rototilling and spatial variations in the samples taken
after the waste application. The metal concentrations calculated to be in
the soils after the waste applications were consistent with the analysed
metal concentrations in the soil samples taken after the waste
applications.
Table 11 summarizes the increases of the soil metal concentration
that were calculated to result from each waste application. The percent-
age values in the table represent the increase over the concentration of
the metal in the soil immediately before the waste application. For
example, the June 1983 waste application to the very high plots increased
aluminum concentration 3.6% over what the concentration was on the soil
sampling data immediately before the June 1983 application.
The June 1982 waste applications did not increase the soil metal
concentrations measurably, except perhaps the calcium, chromium, sodium
and zinc concentrations following the high waste application of that
date. The October 1982 waste applications were greater and the soil metal
concentrations of these four metals and of copper and lead also were
44
-------
TABLE 11. PERCENT INCREASE* IN SOIL METAL CONCENTRATIONS
AS A RESULT OF THE WASTE APPLICATIONS
Date of Waste Application
June 1982
Metal
Al
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Ti
V
Zn
Low
0.03
2
0.5
3
1
0.03
0.06
0.05
0.02
1
0.06
0.7
0.08
0.03
2
Med.
0.06
5
1
5
2
0.05
0.09
0.09
0.04
2
0.1
1
0.1
0.06
It
High
0.1
9
2
10
4
0.09
0.2
0.2
0.07
5
0.2
3
0.3
0.1
8
October 1982
Low
0.5
19
5
20
8
0.3
1
0.6
0.2
5
0.8
8
2
0.5
20
Med.
1
39
8
48
15
0.6
2.4
1.2
0.5
10
1.7
15
3
1
34
High
1.5
56
13
68
24
0.1
3.6
1.8
0.7
16
2.6
24
4
1.5
50
June 1983
Very High
3.6
174
5L
160
93
3.5
5.3
5.1
2.8
95
9
99
12
3.8
133
increase over the concentration of the metal in the soil immediately
before the waste application; values were calculated using the quantity
of waste applied, the metal concentration of the waste, and the metal
concentration in the soil before the application.
45
-------
increased measurably. The very high application of June 1983 increased
Che soil metal concentrations of many of the metals.
The differences also were statistically analyzed to determine when
significant increases occurred. The analyses were a one way ANOVA
followed by Duncan's new multiple range test when significance was found.
The comparison is presented in Table 12 and clearly indicates when the
soil metal concentrations increased significantly.
The increases in calcium undoubtedly resulted in the pH increase of
the high and very high application plots (Figures 9 and 10). Increases in
soil pH increase the immobilization of most metals in the soil.
The increases for chromium, copper and zinc are portrayed in Figures
17 and 18. The soil concentrations of nickel also are presented in Figure
18 to illustrate the type of variations that occurred for a metal that did
not increase in the soil.
The data for several metals (chromium, copper, lead and zinc) that
are of potential environmental concern were evaluated to determine if the
metal concentrations increased over time as a result of the waste applica-
tions. The statistical analysis indicated that the metal concentrations
in the upper 15 cm of the soil did not decrease with time. Example
results are presented in Table 13 for chromium and zinc and in Table 14
for the copper and lead soil concentrations. The data show no change in
the metal concentration for all metals in the natural and rototilled
controls over the entire study.
The immobilization of metals in the soil was analyzed by comparing
the metal concentrations of subsoil samples from the 15 to 30 cm depth
taken in October 1983. The metal concentrations of subsoil samples from
the plots to which the wastes were applied were analyzed statistically to
determine if the deeper soils of the controls and the waste application
plots had different metal concentrations. As of the October 1983 sampling
date, the wastes had been applied to the medium and high application plots
for about one-year and had been applied to the very high application plots
for about four months.
The statistical analysis (Table 15) indicated that sodium was the
only metal that had a significantly different concentration in the 15 to
30 cm depth between the control plots and any waste application plot.
That difference only occurred for sodium in the soil of the very high
plots. Sodium was in high concentrations in the applied waste (Table 2)
and can be a mobile ion under certain conditions. Thus, all of the other
metals were immobilized in the top 15 cm of the plots.
Organics - Soil samples were extracted with methylene chloride and
the extracts analyzed for organics (SECTION 3). Due to time and personnel
constraints, it was impossible to analyze for the organic compounds found
In the oily waste (Table 3). Rather a smaller number of organic compounds
were analyzed in selected soil samples in order to determine the loss of
these compounds after application.
46
-------
TABLE 12. STATISTICAL ANALYSIS* OF THE CHANGES** IN SOIL METAL
CONCENTRATIONS (0-15 cm.) AFTER THE WASTE APPLICATIONS
Difference After
Application of
June 1982
Metal
Al
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Ti
V
Zn
Low
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Med.
0
0
0
0
0
0
0
0
0
0
0
0
0
U
0
High
0
0
0
+
0
0
0
0
0
0
0
0
0
0
0
Difference After Difference After
Application of Application of
October 1982 June 1983
Low
0
0
0
+
0
0
0
0
0
0
0
+
0
u
+
Med.
0
+
0
*
0
0
0
0
0
0
0
*
0
0
*
High Very High
0 0
+
0 +
+
+
0 0
0 +
0 0
0 0
0 +
0 0
+
0 +
0 0
+
* 0 = no significant change (P<0.05) as a result of the waste application
+ = a significant increase (P<0.05) as a result of the waste
application
** change over the concentration of the metal in the soil immediately
before the waste application
47
-------
1OO
120
J
•
a. 80
T>
O
* 4O
a" °
CHROMIUM
5 LOW I HIGH
/ E
£ MEDIUM E VERY HIGH
.
?
•*! ^1 '/I I?
•^1 •/! •/! !^
L •>• •/! i^l !^
t so
Z su
u
8 *o
0
0 30
_l
< 2O
z 10
0
COPPER
. .
•
=
1 I
E S
« •—
= i
E E
X = |
^
M ^
^ ~
^1 = =
! I ! Ill
JUNE 2 JUNE 21 OCT. 5 NOV. B JUNE 6 JUNE 23 OCT. 25
_
y
JUNE
k^iaaa.
=
=
E
S |
M *"
1 L
~
| j
16O
120
80
40
O
i
E
E
E
=
SO
4O
30
2O
10
0
a
__^
FIGURE 17
CHROMIUM AND COPPER CONCENTRATIONS IN THE SOILS OF THE FIELD PLOTS
-------
NICKEL
vO
._ *o
ja 20
X
v 10
9 O
*
.XXXXXXN
!•••••
• Ill
9
E
v 400 r
Z "•w
O
4
* 300
Z
w
o
z
°, 200
o
3
u 100
0
'
•
.
•
.
•
!•••!
\\\\V
Is I
!*
• xl
• /.•
ZINC
- LOW
/
' j
/. MEDIUM
I i I
i I II
il HIGH
_
~
= VERY HIGH
ill if
II i i
__
mm
mm
JJ
•M
=
5
i'< S
4/ =
II I li
JUNE2 JUNE21 OCT.5 NOV.* JUNE 6 JUNE 23 OCT.
—1983
I!
=
mm
^
•V
Z
zz
=
ll
25
I
/
XXXXXXXN
III
30
20
10
0
•
mm •
™
^
mm ™
^^
S
5
=
400
30O
200
10O
9
JUNE 6
--—1984
FIGURE 18
NICKEL AND ZINC CONCENTRATIONS IN THE SOILS OF THE FIELD PLOTS
-------
TABLE 13. AVERAGE CHROMIUM AND ZINC CONCENTRATIONS* IN THE TOP 15 CENTIMETERS OF THE SOIL
OF THE FIELD PLOTS — STATISTICAL ANALYSIS*
Ln
O
Plots
Chromium
Natural Control
Rototllled Control
Low Application
Medium Application
High Application
Very High Application**
Zinc
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Very High Application
6/2/82
3la
31a
29a
30a
31a
—
98a
98a
101a
97a
101a
— —
6/21/82
29a
30a
32a
33a
39a
—
993
98a
105a
104a
120a
— —
10/5/82
27a
27a
29a
29a
33a
—
93a
93a
101a
953
106a
"~~" \
Date of
11/9/82
29a
25a
48b
51b
63b
—
99a
96a
135a
136b
163b
— —
Sample"*""*"
6/6/83 6/21/83
30a
31a
4lb
62b
83C
145a
98a
98a
114a
160b
200b
345a
10/25/83 .
27a
27a
—
A3a
36a
139a
92a
88a
—
120a
107a
325a
6/6/84
30a
29a
—
80b
68b
136a
106a
100a
—
203b
184b
33ia
+ mg/kg soil MFB, n=4.
* data with the same superscript in a horizontal row are not statistically different at the 95% confidence
level (P<0.05).
++ waste applications were in mid-June 1982, late October 1982 and raid-June 1983.
** In June 1983, the low application plots became the very high application plots (see text SECTION 5).
-------
TABLE 14.
AVERAGE COPPER AND LEAD CONCENTRATIONS* IN THE TOP 15 CENTIMETERS OF THE SOIL
OF THE FIELD PLOTS — STATISTICAL ANALYSIS*
Plots
Copper
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Very High Application**
Lead
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Very High Application
6/2/82
14a
15a
14a
15a
16a
—
26a
25a
26a
26a
25a
—
6/21/82
14a
15a
15a
15a
16a
—
26a
27a
27a
27ab
30ab
—
10/5/82
16a
18a
17a
17a
18a
—
24a
23ab
23b
24a
25a
—
Date of
11/9/82
17a
20a
21a
21b
24b
—
25*
25a
31a
32b
35b
—
Sample++
6/6/83 6/21/83
16a
18a
19a
21b
25b
43b
25a
24a
29a
30ab
34 b
53b
10/25/83
16a
15a
—
17a
19a
35b
19b
20ab
—
22a
22a
48b
6/6/84
20a
21a
—
21b
22ab
37b
19b
19b
—
24a
27a
49b
+ mg/kg soil MFB, n=4.
* data with the same superscript in a horizontal row are not statistically different at the 95% confidence
level (P<0.05).
-H- waste applications were in mid-June 1982, late October 1982 and mid-June 1983.
** In June 1983, the low application plots became the very high application plots (see text SECTION 5).
-------
TABLE 15. METAL CONCENTRATIONS* IN SUBSURFACE SOILS (15 TO 30 cm DEPTH)
AT THE FIELD PLOTS
Ul
ro
Metal
Aluminum
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
(continued)
Natural
Control
24 , 400
±1,100
<*
2,900
±900
28
±2
15
±3
28,300
±2,400
18
±3
4,600
±200
560
±190
26
±2
Rototilled
Control
25,200
±2,600
<
3,400
± I , 300
29
±2
16
±3
28,600
±2,200
18
±3
4,600
±200
670
±230
26
±2
Medium
Application
23,500
±1 , 300
<
3,000
±800
27
±2
14
±2
27,700
±2,500
20
±4
4,400
±200
540
±130
25
±2
High
Application
25,500
±1,600
<
3,500
±500
30
±2
16
±2
28 , 300
i 1 , 600
17
±2
4,600
±200
730
±210
27
±2
Very High
Application
27 , 300
±1,500
<
3,600
±1,400
38
±10
17
±2
28,800
±1,700
19
±3
4,800
±100
650
±140
26
±1
F
Value
2.11
-
0.24
2.23
0.36
0.12
0.38
1.35
0.56
0.46
-------
TABLE 15. (continued)
in
Potassium
Sodium
Titanium
Vanadium
Zinc
2,400
±300
84*
±3
74
±19
38
±2
86
±7
2,500
±500
84a
±13
65
±14
38
±4
85
±12
2,200
±500
90a
±27
60
±26
36
±3
82
±6
2,400
±400
105a
±14
70
±7
39
±3
90
±13
3,200
±700
±32
109
±38
42
±3
100
±23
1.85
4.47**
2.05
1.89
0.77
+sampled on October 15, 1983; average and standard deviation, n=4.
*less than limit of detection determined by instrument sensitivity, sample dilution and analytical
matrix interference.
^statistically significant difference (PC0.05) as a result of the very high application data; only the
results for sodium showed any significant differences.
-------
Emphasis was placed on soil samples from the very high application
plots since it was expected that the concentration of organic compounds in
these plots would be well above detection limits and might remain so for a
reasonable period of time. Soil samples from such plots (plots 5 and 12)
were taken shortly after the application in June 1983 and monthly there-
after through October 1983. In addition, soil samples from plot 18 (a
very high plot), plot 14 (a high plot) and plot 11 (a medium plot) were
analyzed at longer time intervals to either confirm the loss patterns from
plots 5 and 12 or to identify the losses in the plots that had received
lower waste applications.
The organic compounds that* were determined in the extracts included
€3 to €26 alkanes, napthalenes and several other aromatics such as fluo-
rene, anthracene, phenanthrene and pyrene. The concentration of these
organics that were found in the soil samples are summarized in Appendix H.
Immediately after the very high waste application, almost all of the
noted organic compounds were present in the soil samples above detection
limits. The organics in the highest concentrations included napthalene
and several methyl-napthalenes, C10 thru C2$ alkanes, and a number of
other aromatics. Less than one month after the very high waste appli-
cation, considerable loss of most of the organics had occurred. Only the
Cm to C25 alkanes could be detected several months after the waste appli-
cation. The chromatograms shown in Figures 19 and 20 illustrate the
changes in organic compounds that occurred.
The data for the high application plot (plot 14) and the medium
application plot (plot 11) indicated the same general pattern as that for
the very high application plots. The C15 to C26 alkanes were present in
the highest concentration. One difference was that no napthalenes or
other aromatics were detected in the soil samples shortly after the high
and medium waste applications. Another noticeable difference is that C16
to C23 alkanes were present at low but detectable concentrations in the
soil of the. high application plot (plot 14) in June 1983, over seven
months after the wastes were applied. These seven months covered the
period of November through May, the colder time of the year. In contrast,
none of the organics could be detected in the soil samples of the very
high plots four months after the very high waste application. These four
months covered the period of June through October, the warmest months of
the year.
Because many of the organic compounds were lost rapidly from the
plots, it was not possible to estimate their loss rates. However, where
two or more concentrations of an organic compound were above the detection
limits, a first order equation was assumed to fit the data and the loss
rates were estimated. Table 16 summarizes the estimated loss rates.
The loss rate constants for the specific organic compounds indicate
that during the warmer months (June through October), the losses were
rapid with half-lives generally less than 30 days. The apparent longer
half-life data for plots 18 and 14 should be considered cautiously since
only two data points were used to calculate the loss rate constants and
54
-------
6/6/83
14 DAYS BEFORE
VERY HIGH APPLICATION
6/23/83
3 DAYS AFTER
VERY HIGH APPLICATION
9/14/83
B8 DAYS AFTER
VERY HIGH APPLICATION
FIGURE 19
CHROMATOGRAMS OF ORGANICS EXTRACTED FROM THE SOIL OF PLOT
A VERY HIGH APPLICATION PLOT
-------
8/13/83
54 DAYS AFTER
VERY HIGH APPLICATION
8/14/83
88 DAYS AFTER
VERY HIGH APPLICATION
10/25/83
127 DAYS AFTER
VERY HIGH APPLICATION
FIGURE 20
CHROMATOGRAMS OF ORGAN1CS EXTRACTED FROM THE SOIL OF PLOT 12
A VERY HIGH APPLICATION PLOT
-------
TABLE 16. ESTIMATED LOSS OF ORGANIC COMPOUNDS IN THE FIELD PLOTS*
Organic Compound
Napthalene
2-methyl-napthalene
1-methyl-napthalene
2 , 6-dimethyl-napthalene
1 , 3-dimethyl-napthalene
2 , 3-dimethyl-napthalene
1 , 2-dimethyl-napthalene
C8 Alkane
Cg Alkane
CIQ Alkane '
C i i Alkane
C12 Alkane
C i 3 Alkane
C1U Alkane
GIS Alkane
C16 Alkane
C17 Alkane
C18 Alkane
Cig Alkane
C20 Alkane
C2i Alkane
C22 Alkane
C23 Alkane
C24 Alkane
C25 Alkane
C2g Alkane
Biphenyl
3-methylbiphenyl
Dibenzofuran
Fluorene
Plot
5
Loss
Rate Calculated
Constant Half-Life
(K.day-1 )* (days)
R**
0.048
0.056
0.094
0.10
0.08
0.07
-
-
R
R
0.06
0.07
0.085
0.028
0.095
0.03
0.03
0.03
0.03
0.078
0.067
0.06
0.06
0.076
0.05
R
R
R
R
-
14
12
7
7
9
10
-
-
-
-
11
10
8
25
7
23
23
23
23
9
10
11
11
9
13
-
-
-
-
Plot 12
Loss
Rate
Constant
(K.day-1
R
0.03
R
R
0.08
0.06
R
-
-
R
R
0.05
0.07
0.04
0.03
0.023
0.024
0.026
0.026
0.025
0.022
0.03
0.026
0.026
0.015
0.02
0.03
0.035
0.04
0.02
Calculated
Half-Life
) (days)
-
23
-
-
9
11
-
-
-
-
-
15
10
18
23
30
29
27
27
28
32
23
27
27
45
34
23
20
17
35
Plot 18
Loss
Rate
Constant
(K.day-1^
R
R
R
R
R
R
R
-
-
-
-
-
R
-
0.005
R
0.005
0.006
0.006
0.006
-
-
0.003
-
-
0.005
-
R
R
-
Calculated
Half-Life
^ (days) I
-
-
-
—
-
-
-
-
-
-
-
-
-
-
138
-
138
115
115
116
-
-
230
-
-
138
-
-
-
-
Plot
14
Loss
Rate Calculated
Constant Half-Life
(K, day"1 )"'"'" (days)
-
-
-
-
-
-
-
—
-
-
-
-
-
-
-
0.005
-
0.006
0.006
0.006
-
0.003
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
—
-
-
-
138
-
115
115
115
-
230
-
-
-
-
-
-
-
-
-------
TABLE 16. (continued)
Phenanthrene
Anthracene
Carbazole
1-Methylphenanthrene
Pyrene
R
R
-
R
0.013 ' 54
R
R
-
0.03
0.007
_ _ _
- - -
_ _ _
23 R -
99
— -
-
-
-
"
'''Plots 5, 12 and 18 are very high application plots, Plot 14 is a high application plot.
"'"'"Only two data points were available to calculate these loss rates and the concentrations of the
second set of data were very close to the detectable limits.
*The loss rate from a first order equation, i.e. Ot = Ooe~Kt where Ot and Oc
-1
**
concentration in the soil (mg/kg MFB) at time t and at time = zero, and K = loss rate constant (day~ )
Rapid - loss to below detectable limits occurred in less than one month after application.
u>
oo
-------
the concentrations of the second data point were very close to the detec-
tion limits of the analytical methods that were used. In contrast, in
plots 5 and 12, there were at least three and as many as five data points
for many of the organic compounds and almost all of the concentrations
were considerably above the detection limits (Appendix H).
Because of the limited data, it was not possible to relate the loss
rate constants to the soil temperature or other factors that might affect
the loss of the organic compounds. The fact that some of the alkanes were
able to be detected in the high application plot (plot 14) after seven
months of cold weather suggests that the loss rates were lower during the
winter months. The loss rates were rapid during the summer months follow-
ing the very high application in June 1983.
The losses for these organic compounds (Table 16) occurred much more
rapidly than did the loss of total oil and grease (Table 8). Whereas the
half-life of these organic compounds was generally less than 30 days, the
half-life of the total oil and grease ranged from 260 to over 400 days.
The difference is caused by other organic compounds that are not lost as
rapidly as the identified compounds but are measured by the oil and grease
analysis.
As discussed earlier, only certain organic compounds were able to be
determined quantitatively in the methylene chloride extracted soil
samples. Although most of these compounds were lost in a short period of
time (several months), other organic compounds remained in the soil for
much longer periods of time (Figures 11, 12, and 13 and Table 9). The
GC/MS preparatory procedures used by RSKERL found considerable quantities
of such residual organics in the extracts. The separation and identifica-
tion procedures suggested the branched alkanes were among such residual
organics. No other specific organics could be adequately separated from
the residual organics and identified.
EARTHWORM DATA
Biomass and Numbers
The average bioraass and numbers of earthworms found in the zone of
incorporation of the field plots are summarized in Appendix I. The
patterns of earthworm bioraass and numbers that occurred throughout the
study are presented in Figures 21 and 22 respectively.
Allolobophora and Lumbricus were the genera of worms that predomi-
nated in the field plots. These are worms commonly found under field
conditions in the eastern United States. They are most commonly found in
the upper soils in the spring and fall when moisture and temperature con-
ditions are more favorable. In reporting the earthworm data, the biomass
data and the numbers of both genera have been combined.
A one-way analysis of variance was performed on the data for each
sampling period to test the null hypothesis that there was no difference
59
-------
ec a
O
3 o
_i
u. w
3°
3 «
2?
a u
1
u
O w
W 3
2 o
200
16O
120
BO
40
•WASTE APPLICATIONS
• NATURAL CONTROL (N)
i ROTOTILLEO CONTROL (C)
(L)
(M)
A S
1882
ONOJ FMAM
FIGURE 21
MEAN VALUES OF WORM B10MASS FOUND IN THE FIELD PLOTS —
SYMBOLS ENCLOSED IN THE SAME BOX INDICATE THAT THE MEANS FROM THOSE
PLOTS ARE NOT SIGNIFICANTLY DIFFERENT (P = 0.05)
-------
TOO
600
"• o
M t SOO
I
K o
O J
* J «OO
Ik
O IL
O
W B 3OO
CD W
w «
ii
W O
200
100
WASTE APPLICATIONS
NATURAL CONTROL (N)
ROTOTILLED CONTOL (C)
LOW (L)
MEDIUM (M)
HIGH (M)
VERY HIGH (V)
111
J J A SONDJ
-1082
FIGURE 22
MEAN VALUES OF THE NUMBERS OF EARTHWORMS FOUND IN THE FIELD PLOTS —-
SYMBOLS ENCLOSED IN THE SAME BOX INDICATE THAT THE MEANS FROM THOSE
PLOTS ARC NOT SIGNIFICANTLY DIFFERENT (P = 0.05)
-------
between the data from the control plots and from the plots that had the
waste applied. When statistical differences at the 5% level (P<0.05) were
observed, Duncan's new multiple range test was used to determine where the
differences were.
The differences that resulted from the statistical analysis are shown
in Figures 21 and 22 in the boxes at the bottom of the figures. Where all
of the types of plots are noted within one box, no statistical difference
(P<0.05) was found between the data from the plots. For example, in May
1982 (Figure 21), there were no significant differences in average biomass
found in any of the type of plots. This was to be expected since at that
time, no waste had been applied to any of the plots and and no rototilling
had occurred.
However, after the waste was applied and rototilling occurred, there
was an impact. As an example, in November 1982, after the second waste
application and the second rototilling, significant differences in average
biomass in the field plots were found (Figure 21). The portrayal of signi-
ficance in Figure 21 for November 1982 indicates that the biomass in the
natural controls was different from that in the rototilled controls and
that the biomass in both types of controls were different from the biomass
in the plots that had received Che wastes. Furthermore, there were no
significant differences in the worm biomass in the plots that had received
the low, medium and high waste applications.
The statistical analyses indicated that the first waste application
and rototilling had little effect on worm biomass and numbers in the field
plots. However, the second rototilling and waste application in October
1982 had a significant effect on both biomass and earthworm numbers.
These differences continued through the remainder of the study.
The very high waste application to the low plots in June 1983 did not
seem to have any significantly different effect on the earthworms than did
the previous application in October 1982. There was a trend of recovery
in biomass and numbers for the medium and high application plots in 1984.
However, there was not a statistically significant difference between the
plots that received the wastes. This lack of significance was due in part
to the large variation in biomass and numbers that occurred between plots
that had the same type of waste application (medium, high or very high).
The trend toward recovery correlates with the data for the artificial
test using soil from the field plots (Table 6). The loss of constituents
in the waste with time reduces the apparent toxicity to the earthworm and
allows the earthworms to repopulate the field plots.
The earthworm density in the natural and rototilled controls tended
to be greater in the spring and fall. This is the time when moisture and
temperature conditions in soil are the most favorable for earthworms in
the top IS cm of soil. This corresponds to earthworm density fluctuations
shown in other studies (13, 14) in the eastern United States.
62
-------
Physical disturbance of the soil, such as rototilling, can have an
adverse impact on earthworms. The lower earthworm numbers and biomass in
the field plots were a result of climatic conditions, rototilling and/or
the applied waste.
Although rototilling did have an impact on the earthworms (Figures 21
and 22), the major impact resulted from climatic factors (temperature and
soil moisture) and from the immediate effect of the waste. There was no
difference in the biomass and numbers between the natural and rototilled
controls until after the second application of waste and the rototilling
in the fall of 1982.
Other information suggests that a single plowing of a grassland does
not necessarily decrease earthworm numbers (15) although repeated cultiva-
tion of grassland can result in a decrease of earthworm populations. The
second rototilling (fall 1982) did cause a significant decrease of the
earthworm numbers and biomass in Che rototilled control plots as compared
to the numbers and biomass in the natural control plots. The data Indi-
cate that mature worms can rebound from a physical disturbance such as
rototilling.
As noted earlier (Figures 14 and 15), after the waste application on
June 1983, the temperatures in the soil of the very high plots were higher
than that of the soil in the other plots. These higher soil temperatures
(24-26°C) also probably were a contributing factor to the low earthworm
populations in the very high plots. The earthworm species found in the
field plots tend to avoid temperatures over 25°C.
Climatic factors such as the temperature and moisture content of soil
have a large impact on the earthworm biomass and numbers found in surface
soils (16). In this study, the worm biomass appeared inversely related to
soil temperature (Figure 23) and appeared reasonably well correlated with
soil moisture (Figure 24). The data indicated that as the temperature in
the upper 13 cm of soil increased, the worm biomass in the natural
controls decreased. The same relationship was found for worm numbers.
The application of the wastes had definite impacts on earthworm
numbers and biomass in the field plots. The impacts were due to roto-
tilling and the immediate effect of the applied waste. The significance
of the impacts varied. However, the impacts and the pattern of change can
be summarized by the conceptual model shown in Figure 25.
The earthworm population was not significantly different among plots
prior to the initial rototilling and first waste application. The earth-
worm biomass and numbers decreased somewhat due to the rototilling and
decreased more so due to the immediate effect of the applied waste. The
recovery from the rototilling was fairly rapid. However, the recovery
from the immediate effect of the applied waste (treatment effect) took a
much longer period of time. These impacts are in addition to the natural
changes in worm biomass and numbers that occur due to changes in climatic
conditions (Figures 23 and 24).
63
-------
NATURAL CONTROL PLOTS
* ^r
Ȥ
o 3
TJ
X
TCUPCRATURI
JJ ASOMDJ FMAMJJ AS ONDJ f MAMJ J
FIGURE 23
COMPARISON OF EARTHWORM B10MASS AND SOIL TEMPERATURE IN THE FIELD PLOTS
-------
(S
2OO
ieo
120
80
a*
IB a
4 J
w u
H
w
O W
4 Z «0
K »-
W
> Z
NATURAL CONTROL PLOTS
SOIL
3
•
O
M
H
O
a <
M JJASOMOJFMAMJJASOHDJFMAMJJ
IB63 • • 1083 19B4
FIGURE 24
COMPARISON Or EARTHWORM BIOMASS AND SOIL MOISTURE IN THE FIELD PLOTS
-------
N - NATURAL CONTROL
C - ROTOTILLEO CONTROL
L - LOW
M - MEDIUM
H - HIGH
WASTE TREATMENT
RECOVERY TIME
L
M
N
C
L
M
H
WASTE
APPLICATION
ROTOTILL EFFECT -
TREATMENT EFFECT'
N
L
M
ROTOTILLING
RECOVERY
TIME
FIGURE 25
A GENERAL CONCEPTUAL MODEL OF THE IMPACT TO AND RECOVERY OF
SOIL BIOTA WHEN WASTES ARE APPLIED TO THE SOIL
66
-------
The results suggest that soil biota such as earthworms can recover
from single, even large applications of an oily waste of the type used in
this study. With time and no other impacts, the earthworm population in
all the field plots should again become similar to that in the natural
control plots.
Bioaccumulation
The bioaccumulation of metals and organics in an applied waste by
earthworms is of environmental interest because the worms can serve as a
food source for higher forms of life such as mice, moles and other small
mammals and birds. The concentrations of metals and organics in the soil
and the worms were analyzed to determine if any bioaccumulation resulted
from the application of the wastes. The concentrations of metals found in
the worms are summarized in Appendix J.
In analyzing the metal and organic content of the worms, the entire
worm was used including the content of the gut. This was done since it is
the entire worm that may be eaten by birds and small animals. Because Che
interest was to identify the bioaccumulation that might occur and the
potential impact on other parts of the ecosystem, it was appropriate to
consider the entire worm. The worms were washed, however, to remove any
soil or other material that inay have adhered to the skin.
The gut content of the worm will include some of the soil surrounding
the worm. In interpreting the bioaccumulation data, it should be recog-
nized that the data represent both earthworm blomass and the soil and
other material in the gut of the earthworm.
Metals - The concentrations of metals found in the earthworms on the
noted sampling dates were not as extensive as that of the soil metal
concentrations because, on many of the sampling dates, there were few or
no worms.
The data for several metals (chromium, copper, lead and zinc) that
are of potential environmental concern were evaluated to determine if
there were any statistically different concentrations in the worms as a
result of the waste applications. Example results are presented in Table
17 for chromium and zinc and in Table 18 for copper and Lead.
In June 1983, the low application plots became the very high applica-
tion plots (SECTION 5). However, because of the very high waste applica-
tion of June 1983, worms were not found in the very high plots for a
considerable period of time after the application. Data on the metal
concentrations in the earthworms of the very high plots were obtained only
in June 1984. In the statistical analyses (Tables 17 and 18), the very
high worm metal concentrations were included with the low application data
to see if any differences could be ascertained.
The analyses indicate that only the chromium concentration of the
earthworms increased as a result of the waste applications. Except for
chromium, the concentrations of copper, lead and zinc in the worms of the
67
-------
TABLE 17. AVERAGE CHROMIUM AND ZINC CONCENTRATIONS* IN THE EARTHWORMS
OF THE FIELD PLOTS — STATISTICAL ANALYSIS*
00
Plots
Chromium
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Zinc
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
6/2/82
9.7a
7.4a
6.2a
6.8a
8.2a
222a
305a
255a
225a
225a
6/21/82
7.8a
15. 3a
13. 8a
10. 7a
7.4a
258a
278a
323d
241a
248a
Da
10/5/82
10. 2a
13. 3a
11. 4a
12. 7a
19. 2b
223a
183a
248a
24 3a
220a
te of Sample"*"
11/9/82
8.3a
8.5a
8.0a
10. 8a
ND
238a
350a
225a
433a
240a
+
6/6/83
11. Oa
16. Oa
30. Oa
18. Ob
21. Ob
290a
250a
300a
230a
198a
10/25/83
12. 5a
12. 3a
ND
20. Ob
18. 5b
269a
221a
ND
218a
202a
6/6/84
10. Oa
11. 5a
37. 9a**
18. 8b
21. 5b
258a
232a
866a**
279a
387a
+ mg/kg moisture free earthworm tissue and gut contents; the number of worms collected and analyzed on
each sampling date were not constant - on many sampling dates, few worms were found; ND = below
detection limits for the quantity of sample obtained on that date or else no worms found.
* data with the same superscript in a horizontal row are not statistically different at the 95% confidence
level (P<0.05).
++ waste applications were in mid-June 1982, late October 1982 and mld-.Iune 1983.
** In June 1983, the low application plots became the very high application plots (see text, SECTION 5).
-------
TABLE 18. AVERAGE COPPER AND LEAD CONCENTRATIONS* IN THE EARTHWORMS
OF THE FIELD PLOTS — STATISTICAL ANALYSIS*
VO
Plots
Copper
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Lead
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
6/2/82
11. 8a
12. Oa
11. 2a
9.6a
11. 5a
12. Oa
10. 5a
9.8a
8.0a
8.3a
6/21/82
11. 4a
28. 6a
20. Oa
16. la
12. 2a
8.5a
6.3a
9.0a
19. Oa
10. 5a
Da
10/5/82
11. 8a
13. Oa
13. Oa
36. 3a
15. 5a
12. 7a
14. 7a
16. 3a
16. 3a
18. Oa
te of Sample"1"
11/9/82
12. 2a
11. Oa
16. 7a
ll.5a
tJD
14. 5a
15. la
15. Oa
12. Oa
ND
+
6/6/83
12. Oa
12. Oa
26. Oa
17. Oa
12. Oa
8.6a
13. 2a
13. 5a
14. 3a
15. 5a
10/25/83
10. 3a
11. Oa
ND
12. Oa
14. 5a
8.8a
8.8a
ND
ND
15. Oa
6/6/84
10. 7a
10. 5a
14. 3a**
12. Oa
13. 5a
7.8a
8.0a
ND **
10. 3a
10. 3a
+ rag/kg moisture free earthworm tissue and gut contents; the number of worms collected and analyzed on
each sampling date were not constant - on many sampling dates, few worms were found; ND = below
detection limits for the quantity of sample obtained on that date or else no worms found.
* data with the same superscript in a horizontal row are not statistically different at the 95% confidence
level (P<0.05).
++ waste applications were in mid-June 1982, late October 1982 ami mid-June 1983.
** In June 1983, the low application plots became the very high application plots (see text, SECTION 5).
-------
control plots were statistically the same as that of worms of the plots
that received the waste applications.
In a similar manner, the concentration of all of the metals were
compared using a one way ANOVA to identify if there were any significant
differences in the earthworm concentrations of other metals over the
entire project period. The comparison is presented in Table 19. The
analysis indicates that there were several situations in which there were
significant differences. There was no obvious pattern to the differences
however. Earthworms from the rototilled controls had significant differ-
ences of aluminum, iron, nickel and vanadium whereas the worms from the
high application plots had significant differences for aluminum, chromium,
and titanium. Because of the lack of a pattern, such as differences
always showing up in the plots with the higher waste applications, it may
be that the differences noted in Table 19 are due to normal differences in
metal concentrations in earthworms.
The bioaccuraulation of metals that occurs is of interest since worms
are a part of the food chain. Table 20 summarizes the range of metal bio-
accumulation that was found in the earthworm tissue. In this table, bio-
accumulation is defined as the ratio of the metal concentration in the
earthworm to the metal concentration in the soil of the plot from which
the earthworm was obtained. Bioaccumulation factors greater than one
indicated that the metal was being selectively accumulated by the
earthworm. Factors slightly over one should not be considered important
because of the data variations that may have been caused by sampling and
analytical variations and because this factor is a ratio. Bioaccumulation
factors that are much larger than one are relevant and indicate that bio-
accumulation has occurred.
Based on the data in Table 20, the earthworms accumulated cadmium,
potassium, sodium and zinc. Potassium and sodium are of physiological
but not environmental importance in terms of bioaccumulation.
Cadmium bioaccumulates in earthworms to a greater degree than any
other metal. The bioaccumulation factor of cadmium in earthworm tissue
rarely was less than two and commonly was greater than 20.
For comparative purposes, the bioaccumulation of cadmium, copper,
zinc and lead by earthworms as found by other investigations is summarized
in Table 21. Because of the large amount of information available in each
paper, the ranges of bioaccumulation data are indicated. As noted from
Table 21, the bioaccumulation data obtained in this study were similar to
that reported by other investigators.
The bioaccumulation factors for other metals can be compared to fac-
tors identified in a recent comprehensive study (Table 22). Generally the
factors in Table 22 are less than those reported in this study.
70
-------
TABLE 19. STATISTICAL EVALUATION"*" OF THE EARTHWORM METAL CONCENTRATIONS
DURING THE PROJECT PERIOD (F VALUES)
Metal
Al
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Ti
V
Zn
Natural
Control •
Plots
1.87
0.50
1.24
1.86
0.53
1.14
1.10
0.68
0.81
1.43
2.39
1.87
1.98
3.13*
0.59
Rototllled
Control
Plots
12.3*
2.16
1.40
0.55
0.84
10.9*
1.60
2.17
1.94
1.80
5.92*
2.05
1.87
8.46*
1.15
Low""
Application
Plots
2.47
2.20
2.16
2.92
1.35
3.46*
1.02
4.45*
1.78
3.99*
0.89
1.62
7.93*
3.12
2.54
Medium
Application
Plots
2.38
2.10
0.85
4.80*
1.19
1.52
1.16
2.48
1.01
0.87
3.4'9*
1.17
2.35
5.47*
1.06
High
Application
Plots
5.82*
2.70
0.83
3.74*
1.24
2.71
1.85
2.24
0.8R
2.00
2.39
2.69
6.25*
3.03
2.82
+ One way ANOVA using all of the earthworm data from the respective plots
(Appendix).
++ In June 1983, the low application plots became the very high applica-
tion plots (see text, SECTION 5). The data for 6/6/84 from the very
high plots was included with the data from the low plots.
* indicates significance at the 5% level (P<0.05)
71
-------
TABLE 20. BIOACCUMULATION+ OF METALS BY EARTHWORMS*f
N>
Metal
Al
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Ti
V
Zn
June 1982
0.12-0.29
0.70-1.20
8.0-14.4
0.20-0.30
0.75-1.91
0.21-0.36
1.70-2.65
0.36-0.45
0.18-0.34
10.3-16.6
'0.23-0.54
0.30-0.70
0.23-0.83
0.19-0.38
1.20-2.10
Date
November 1982
0.24-0.30 '
0.62-1.70
5.9-11.5
0.16-0.34
0.55-0.79
0.30-0.51
2.03-3.73
0.43-0.59
0.26-0.46
4.5-8.7
0.41-0.48
0.38-0.60
0.28-0.42
0.20-0.29
1.5-3.7
of Sampling
June 1983
0.30-0.43
0.48-1.12
14.0-29.6
0.26-0.58
0.48-1.73
0.33-0.46
0.97-2.13
0.46-0.56
0.28-0.43
9.6-21.6
0.64-0.77
0.36-1.04
0.50-1.01
0. 36-0. 47
0.99-2.95
October 1983
0.34-0.42
0.98-1.12
NA*
0.45-0.51
0.65-0.79
0.37-0.44
1.01-2.42
0.49-0.58
0.34-0.42
23.0-32.0
0.46-0.70
0.45-0.68
0.60-0.85
0.44-0.57
1.81-2.92
June 1984
0.11-0.37
0.45-1.04
6.6-10.3
0.25-0.42
0.42-0.72
0.20-0.40
0.89-3.06
0.33-0.49
0.23-0.41
6.7-67.7
0.35-0.73
0.37-0.43
0.45-0.86
0.30-0.39
1.66-2.55
+ Ratio of the metal concentration in the earthworm to the metal concentration in
Che soil of the plots from which the earthworms were obtained.
++ Range of data from soil and worm samples 'collected on noted dates; numbers
represent the range of mean values (n = 4) from each type of plot (controls, low,
medium, high, very high).
* NA - not available, not enough tissue available for analysis.
-------
TABLE 21. EARTHWORM BIOACCUMULATION FACTORS FOR CADMIUM, COPPliR, LEAD AND ZINC.*
Cadmium
—
11.6-22.5
7.0-15.2
11.6-22.5
—
2.9-12.6
— •
3.8-5.0
—
17.1-31.1
8.8-151.4
1-7.5
4.6-6.3
1.8-15.0
3.9-35.0
18-156
Metal
Copper Lead
1 0.2
—
0.5-1.2
0.1-0.3
0.8-2.4
—
0.9-1.3
0.4
0.4-1.5
0.6-0.8 0.4-0.5
0.1-0.8
0-2.7
0.2-0.3
0.3-4.9 1.4-9.2
0.2-0.5
—
Zinc
—
3.1-13.4
2.2-8.1
3.1-13.5
0.3-0.7
—
1.6-2.4
0.5
—
7.3-17.5
—
0.7-5.4
2.2-3.7
—
1.0-10.3
1.4-4.1
Reference
17
18
»
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Data from other investigations.
-------
TABLE 22. EARTHWORM BIOACCUMULATION FACTORS FOR SEVERAL METALS*
Range of Range of
Metal Reported Data Metal Reported Data
Ca
Cr
Fe
0.4-0.7
0.03-0.11
0.02-0.25
K
Mn
Na
0.40-0.53
0.02-0.22
0.59-0.88
*From reference 32
The data indicate that, of all the metals of potential concern, cad-
mium bioaccumulates to a greater extent. Only the very high waste appli-
cation increased the cadmium concentration of the soil significantly
(Tables 11 and 12). The cadmium that accumulated in the earthworm tissue
probably came more from the background cadmium in the soil than from the
cadmium in the applied waste, especially since the cadmium bioaccumulation
occurred at comparably high levels in the worms from the control plots.
Increased concentrations of chromium, copper, lead and zinc occurred
in the soil as a result of the waste applications (Table 12). However,
none of these metals bioaccumulated in earthworms to any greater extent
than was found in other studies (Tables 21 and 22) or in earthworms from
the control plots.
Thus, it appears that the application of these oily wastes did not
cause any abnormal or unexpected bioaccumulation of metals in earthworms.
It is also apparent that earthworms bioaccumulate few of the metals found
in soils.
Or-ganics - The earthworm sample extracts were analyzed for the same
organic compounds that were determined for the soil extracts (Table 16).
None of these compounds were found in any of the earthworm extracts at
concentrations greater than the detection limits for these compounds. The
detectable limits were 10 ng/ul when the analytical methods at RSKERL were
used. These results suggest that earthworms do not accumulate any of the
noted organic compounds.
MICROARTHROPODS
Soil animals are an integral part of any soil system and play a major
role in the initial formation of soils and in the continued decomposition
of organics. Investigations of soil microarthropods, primarily of mites
and collembolans, have become increasingly important in the study of
ecosystem perturbations. These microarthropods are: (a) numerous, with
usually several hundreds of thousands of individuals per square meter In
non-cultivated soils, (b) taxonomically diverse, with 100 to 200 species
represented in habitats such as old fields, (c) trophlcally diverse and
74
-------
include species which are predaceous, parasitic, fungivorous or detriti-
vorous, (d) relatively easy to collect and preserve and (e) significant
functional components of soil communities..
Four principal groups of soil microarthropods were examined. One was
the insect order Collembola (collembolans or springtails) which feed
principally on soil fungi or organic detritus, although a few are faculta-
tive or obligatory predators of soil nematodes or other soil organisms.
The other three were suborders of mites which are important in soils.
These are the Oribatida (detrivores or fungivores); the Mesostigmata
(predators of Collembola, other mites, or soil nematodes); and the
Prostigmata (heterogeneous, fungivores, predators or parasites of other
soil animals). These soil organisms were chosen because they are
numerically dominant in soil ecosystems.
Soil samples containing microarthropods were collected only during
the first project year. The sampling dates are noted in Table 23. Three
cores were removed from each plot on each sampling date for a total of
sixty samples on each date. The sampling points were determined at random
and were different from those used for the earthworm and soil samples. No
subplots were sampled more than once. To avoid trampling effects, all
subplots were sampled from a portable wooden spanning bridge. Cores were
not directly handled. They were left in the aluminum corer and placed
into individual plastic bags which were then deposited in styrofoatn
ice-chests. Extraction began within three hours of collection.
The procedures used to extract and identify the microarthropods are
presented in Appendix A.
For analyses using parametric statistics such as ANOVA and multiple
comparison tests, the numbers of individuals per sample for each species
TABLE 23. SOIL MICROARTHROPOD SAMPLING DATES
1982
June 2 September 13
June 9-10 October L2
June 22 October 22-23
July 14 November 12
August 13 December 2
1983
March 15
June 8
July 8
were subjected to a log-transformation (nt = Iog10 (n+1)) prior to ana-
lysis. This is a standard technique (33, 34) for eliminating the problem
of having sample variances which change with each sample (heterogeneity of
75
-------
variance), a condition which violates an important assumption of
parametric tests. This technique "normalizes" the data without changing
its information content. Heterogeneity of variance is inherent in analy-
zing the density of most organisms because of their aggregated, rather
than random spatial distributions. This is especially true of micro-
arthropods and other soil organisms (35, 36). Transformed means can be
returned to numbers reflecting "real individuals" by taking the antilog of
the mean and subtracting one.
A one-way analysis of variance (ANOVA) procedure was performed at
each sampling period to test the hypothesis that there was no difference
between means for the various treatments and controls. When statistical
significance differences (P £ 0.05) were noted, the ANOVA was followed by
a Student-Newman-Keuls (SNK) multiple comparison test to determine which
pairs of treatments were significantly different with regard to mean
density of that particular species. Similar analyses were performed for
certain higher taxonomic groups, in which the data for individual species
were pooled.
Results - The pooled numbers for the four major groups during all
sampling periods are given in Table 24. Overall, Prostigmata were the
most prevalent microarthropods sampled, while the Mesostigmata were the
lowest in density. In terms of average number of microarthropods per
meter2, there were fewer organisms in the plots that were tilled and had
the wastes applied. In general, as the application rate increased, the
number of organisms per meter2 decreased. Table 25 expresses these over-
all decreases as percentages of natural control plot results.
Figure 26 illustrates the total microarthropod pattern as a function
of time. The impact of rototilling and the oil waste appears temporary.
The total microarthropod density in the natural control plots varied
little over time. There were no significant differences between plots
before Che June 1982 application. However, there was a significant roto-
tilling and- treatment effect after the June and October applications.
The rototilling effect from the June 1982 application was short with
recovery occurring after one month. The rototilling effect from the
October 1982 application was equally strong but the organisms did not
recover until some time between March and June 1983. This slow recovery
probably was due to the cold weather after the October 1982 treatment.
Following the June 1982 rototilling and waste application, recovery
of microarthropod densities was gradual but complete within four months.
By mid-October 1982, all plots had total microarthropod densities similar
to those of natural controls (Figure 26). The October 1982 rototilling
and waste application effects were initially equally as great, but
recovery was slower because of the colder temperatures during the winter
of 1982-83 and was not complete when the microarthropod evaluation ended
in July 1983.
The Impact of rototilling and waste application on the dominant
species of microarthropods is summarized in Table 26. Although
76
-------
TABLE 24. TOTAL NUMBERS OF MICROARTHROPODS COLLECTED AT THE FIELD PLOTS
DURING JUNE 1982 TO JULY 1983
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Total
Collembola Mesostigmata Oribatida Prost.igmata
2,740 688 ' 2,770 6,340
1,490 485 2,340 5,510
572 327 538 1,480
258 294 257 1,730
150 438 262 1,090
5,210 2,232 6,167 16,150
Average Number
Total per meter
12,538
9,825
2,917
2,539
1,940
29,759
58,000
46,900
13,200
11,600
8,840
138,540
TABLE 25. MICROARTHROPODS IN THE FIELD PLOTS EXPRESSED
AS % OF NATURAL CONTROL PLOT NUMBERS*
Natural Control
Rototilled Control
Low Application
Medium Application
High Application
Collembola Mesostigmata Or i bat Ida
—
54% 70% 84%
21% 48% 19%
9% 43% 9%
5% 64% 9%
Prostigmata
—
87%
23%
27%
17%
Total
—
78%
23%
20%
15%
*Data from Table 24
-------
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00
u
_l
Q.
Z
<
I/I
£
k
0
•
C
M
O
>
O
Z
u.
O
K
Ul
O
Z
3
Z
U
Z
2.4
WASTE APPLICATION AND
ROTOTILLINQ
WASTE APPLICATION AND
FIOTOTILLING FOR
VERY HIGH PLOTS
ONLY
2.0
1.6
1 2
0.8
O.4
PRT
N
M
0
!H
1C
iM
N
C
L
H
LM
1*1
l£
L
[M
L«
C
N
L
M
H
1982
N
C
M
H
L
1
VI
N
C
L
M
H
j
N
C
M
H
V
FIGURE 26
MEAN TOTAL MICROARTHROPODS (MITES AND COLLEMBOLANS) COLLECTED AT THE FIELD
PLOTS — DATA TRANSFORMATION IS LOGio (n + 1) -- SYMBOLS ENCLOSED IN THE
SAME BOX INDICATE THAT THE MEANS FROM THOSE PLOTS ARE NOT SIGNIFICANTLY
DIFFERENT (P = 0.05)
-------
TABLE 26. IMPACT OF ROTOTILLING AND OILY WASTE APPLICATION
ON MICROARTHROPOD SPECIES IN FIELD PLOTS
First Application Second Application
(June 1982) (October 1982)
Rototill Waste Rototill
Effect Effect Effect
COLLEMBOLA
Isotoma notabilis
Isotomiella minor
Folsomia fimetaria
Isotomurus palustris
ONYCHIURIDAE (pooled)
ENTOMOBRYIDAE (pooled)
SMINTHURIDAE (pooled)
ORIBATIDA
Schelori bates laevigatus
Tectocepheus velatus
Punctoribates armipes
-(d)
+ (d)
-(i)
+ (d)
-(d)
-(i)
-(i)
-(i)
-(i)
+ (d)
Oppiella nova 0
BRACHYCHTHONIIDAE (pooled) -(d)
PROSTIGMATA
Scutacarus sp. A -(i)
Bakerdania sp. A
Bakerdania sp. E
Tarsonemus sp.
Benoinyssus sp. A
Cocceupodes sp. B
Tydeus sp. A
Microtydeiis sp.
Coccotydeus sp.
Alicorhaeia sp.
MESOSTIGMATA
Paragamasus sp.
Rhodacarus sp.
Rhodacarellus sp.
Arctoseius cetratus
+ = density significantly
- = density significantly
0 = no significant change.
i = immediate effect.
d - delayed appearance of
species.
m = delayed appearance of
* = densities were higher
-(i)
+ (d)
-U)
-(i)
0
-(d)
0
+ (d)
0
-(d)
0
-(d)
+ (d)
-(m)
0
0
0
0
0
-(i)
-(m)
-(m)
0
0
0
0
0
0
-(m)
-(m)
-(m)
0
-(d)
-(d)
0
0
0
0
+ (d)
-(d)
-(i)
-(i)
-(d)
-(i)
-(d)
-d)
0
-(i)
0*
+(d)
-(d)
-(i)
-(i)
+ (i)
-(d)
-(i)
-(i)
-(d)
-(d)
0
-(d)
-(i)
0
-(d)
+ (i)
(P = .05) increased.
(P = .05) decreased.
effect due to prior (seasonal) absence
treatment effect due to strong rototill
in Control plots, but not significantly
79
Waste
Effect
-(i)
-(m)
0
0
0
-(i)
-(i)
-(0
-(m)
0
-(d)
0
0
0
0
-(i)
-d)
-(m)
-(i)
-(i)
-(d)
-(d)
-(m)
0
0
-(i)
of
effect.
so.
-------
rototilling decreased the numbers of most species, it had a positive
effect on a few species. The application of the waste had an almost
universal negative impact on the microarthropods.
The land treatment of the wastes and the climatic conditions had an
effect on the soil microarthropod community that was similar to that noted
for the earthworms. Soil temperature and moisture, rototilling, and the
applied waste all had an effect on the microarthropod population. The
significance of these impacts, and the time necessary for recovery varied
with both the microarthropod population being measured and with the taxo-
noraic group. The conceptual model presented for the earthworms (Figure
25) also can be applied to the microarthropod data. The microarthropod
density was not significantly different between plots prior to rototilling
and waste application. The population was decreased by the rototilling
and decreased even more so by the waste application (treatment effect).
The recovery from the rototilling generally preceded recovery from the
treatment effect. With time and no other impacts, the microarthropod
population should become similar for all the field plots.
Negative impacts of cultivation on soil microarthropods have been
noted by a number of workers, mostly in Europe (37-39). Two reasons for
the negative impacts have been proposed. First, physical abrasion suffer-
ed during cultivation may damage or kill the animals. This is isuch more
likely to be a problem with larger animals, such as earthworms. A second,
and intuitively more important probable cause of observed decreases, is
the production of unstable microclimates. Removal or incorporation of the
thick vegetation and litter, characteristic of pastures and old-fields,
eliminates an effective natural insulator. Marked temperature, pH and
moisture fluctuations did occur in this study (Figures LO, 14 and 16).
Microarthropods are generally adapted to living in a highly structured,
spatially heterogeneous physical environment with a relatively homogeneous
microclimate. As a result of cultivation (rototilling), this relationship
is reversed making the soil more homogeneous and the microclimate hetero-
geneous and unstable.
The reason for the immediate effect of the wastes on microarthropods
is not clear. Clear negative impacts on community structure were noted
for all major groups except the Mesostigmata, and the possible reasons for
these impacts are several. First, there may be a direct toxicity to the
animals. If any microarthropods were to show toxicity it would probably
be the Mesostigmata, which are active predators utilizing larger volumes
of soil in their movements than other mites. However, they are the one
group which was not significantly affected by the waste application.
The immediate impact of the waste appeared to be independent of the
application rate. Densities and other community parameters were generally
depressed as much by low treatments in June 1982 as by the very high
treatment in June 1983, which was about 56 times greater. The tests for
significance also revealed few taxa or times when the various rates had
different effects.
80
-------
In summary, the application of the oily wastes to an old-field site
in central New York State had a predominantly negative impact on the soil
microarthropods. This impact was due to both the application method
(rototilling) and to the immediate effect of the oily waste.
The negative impact of rototilling was temporary, with recovery of
the microarthropod population occurring within 1-3 months after late
spring rototilling and between 6-8 months after the fall rototilling. The
negative impacts of the oily waste were more long-lived. Total density
recovery did not occur during the time frame of the study. Multiple
applications per year would probably keep the system in a highly disrupted
state.
Microarthropod densities were affected by the waste application.
However, differences between application rates were observed mainly in the
recovery with lower waste applications allowing faster recovery.
Perhaps the most significant general result of this aspect of the
project is that an important group of soil organisms (microarthropods)
does recover from modest inputs of oily wastes. When use of a land treat-
ment site is discontinued, "reclamation" by soil microarthropods is likely
to occur, although at a rate not presently predictable.
81
-------
REFERENCES
1. Brown, K. W. and Associates, "A Survey of Existing Hazardous Waste
Land Treatment Facilities in the United States", Report prepared for
the U.S. Environmental Protection Agency. Contract 68-03-2943,
August 1981.
2. Beak Consultants Limited, Landspreading of Sludges at Canadian
Petroleum Facilities. Petroleum Association for Conservation of the
Canadian Environment, Report 81-5A, December 1981.
3. Standard Methods for the Examination of Water and Wastewater, 15th
edition. American Public Health Association, Washington, D.C., 1980.
4. Black, C. A., Evans, D. D., White, J. C., Ensminger, L. E., and
Clark, F. E., Methods of Soil Analysis, American Association of
Agronomy, Inc., Madison, Wisconsin, 1965.
5. American Society For Testing Materials, Annual Book of ASTM
Standards, ASTM, Philadelphia, Pa. 1980.
6. McKenzie, H. A. and Wallace, H. S. "The Kjeldahl Determination of
Nitrogen: A Critical Study of Digestion Conditions - Temperature,
Catalyst and Oxidizing Agent", Australian J. Chemistry 7, 55-71,
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12. Raymond, R. L., Hudson, J. 0., and Jamison, V. W. "Oil Degradation
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13. Hopp, H. "The Ecology of Earthworms in Cropland." Soil Sci. Soc_.
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15. Evans, A. C. and Guild, W. J. "Studies on the Relationships Between
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16. Edwards, C. A. and J. R. Lofty. "Effects of Cultivation on Earthworm
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17. Williamson, P. and Evans, P. R. "Lead Levels in Roadside Inverte-
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18. Anderson, S. H. "Environmental Monitoring of Toxic Materials in
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23. Ireland, M. P. "Excretion of Lead, Zinc and Calcium by the Earthworm
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25. Van Rhee, J. A. "Effects of Soil Pollution on Earthworms."
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27. Andersen, C. "Cadmium, Lead and Calcium Content, Number and Biomass,
in Earthworms (Lumbricidae) from Sewage Sludge Treated Soil."
Pedobiologia, _T9> 309-319, 1979.
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rubellus, Dedrobaena veneta and Eiseniella tetraedra Living in Heavy
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Earthworms from Pasture in the Vicinity of an Industrial Smelting
Complex." Environ. Pollut., 23A, 313-321, 1980.
32. Helmke, P. A., Robarge, W. P., Korotev, R. L. and Schomberg, P. J.
"Effects of Soil-applied Sewage Sludge on Concentrations of Elements
in Earthworms." J_. Environ. Qual., 8^ 322-327, 1979.
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99-113, 1949.
84
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APPENDIX
TABLE OF CONTENTS
A Mlcroarthropod Extraction and Identification Procedures
B Methods Used to Prepare Soil and Earthworm Samples for Analysis by
RSKERL
C Spatial Variability of the Soil Samples from the Field Plots
D Analytical Method for the Determination of Oil and Grease in Soil
Samples
E Cation Exchange Capacity of the Soil in the Field Plots
F Summary of Average Chemical and Physical Parameters for the Field
Plots
F-l Natural Control Plots
F-2 Rototilled Control Plots
F-3 Low Application Plots
F-4 Medium Application Plots
F-5 High Application Plots
F-6 Very High Application Plots
G Metal Concentrations in the Soils of the Field Plots
G-l Natural Control Plots
G-2 Rototilled Control Plots
G-3 Low Application Plots
G-4 Medium Application Plots
G-5 High Application Plots
G-6 Very High Application Plots
H Organic Concentrations in the Soils of the Field Plots
H-l Plot 5 - A Very High Application Plot
H-2 Plot 12 - A Very High Application Plot
H-3 Plot 18 - A Very High Application Plot
H-4 Plot 14 - A High Application Plot
H-5 Plot 11 - A Medium Application Plot
I Average Earthworm Numbers and Biomass in the Field Plots
1-1 Earthworm Numbers
1-2 Earthworm Biomass
85
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Metal Concentrations in the Earthworms from the Field Plots
J-l Natural Control Plots
J-2 Rototilled Control Plots
J-3 Low Application Plots
J-A Medium Application Plots
J-5 High Application Plots
J-6 Very High Application Plots
Quality Assurance Analyses of the Standard Sludge Supplied by the
Project Officer - Oil and Grease Results
86
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APPENDIX A
MICROARTHROPOD EXTRACTION AND IDENTIFICATION PROCEDURES
The aluminum corer containing the soil sample was inverted and heat
from a 7 watt light bulb was applied from above. As drying proceeds ver-
tically down the core, a critical relative humidity is reached at which
point the microarthropods travel to the bottom end of the core (originally
the soil surface) where they fall into a vial filled with preservative
(70% ethanol). The extraction occurred in a temperature-controlled room
with an ambient temperature of 5°C. Extractors were left undisturbed for
one week. Even the wettest samples had dried by this time. Most of the
microarthropods emerged during the first 2 or 3 days of extraction. Vials
containing preserved microarthropods were stored until the remaining steps
could be accomplished.
The microarthropod identification steps were highly labor-intensive.
The contents of each vial were carefully sorted under magnifications of 10
to 40 diameters to separate microarthropods from small particles of soil
and organic debris which invariably fall into the preservative. Specimens
were sorted into four major taxonomic categories: collembolans, mesostig-
matid mites, prostigmatid mites, and oribatid mites. The first three
groups were mounted on microscope slides for counting and identification.
Because of low diversity and high familiarity, the oribatid mites were
processed in alcohol. Identifications were made at the species level. If
a species could not be identified, it was given an arbitrary letter
designation.
87
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APPENDIX B
METHODS* USED TO PREPARE SOIL AND EARTHWORM SAMPLES
FOR ANALYSIS BY RSKERL
A. Extraction Procedure For Soil Organics
• Ten grams of the "as is" soil were mixed with ten grams of
anhydrous
• The mixture was extracted in acid washed glass equipment for two
hours or at least 20 cycles with 200 ml methylene chloride,
concentrated to about 2 to 3 ml and shipped to RSKERL in glass
vials.
B. Preparation For Soil Metal Analyses
• Oven dried soil samples were ground to 20 mesh.
• About LOO grams of each sample were shipped to RSKERL in glass
bottles.
C. Preparation For Earthworm Metal Analysis
• Earthworm tissue samples were oven dried at 60°C for 24 hours,
finely ground using porcelain equipment and shipped to RSKERL in
glass bottles.
D. Extraction Procedure for Organics Ln_ Earthworm Tissue
• Fresh earthworm tissue was mixed with ten grams of anhydrous Ma 2 SO ^
and extracted with 200 ml of methylene chloride for two hours. The
extract was concentrated to about 2 to 3 ml and shipped to RSKERL
in glass vials.
*Details of the methods were supplied to project investigators by the
RSKERL project officer.
88
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APPENDIX C
SPATIAL VARIABILITY OF THE SOIL SAMPLES
FROM THE FIELD PLOTS
Introduction
This study was undertaken to determine the extent to which the
variability of the data was due to the non-homogeneity of waste
application and rototilling at the field plots. At each plot, three
random core samples were taken from the plots periodically for analysis
(SECTION 3). In addition, every attempt was made to use plots with
comparable soil characteristics, to distribute the wastes uniformly, and
to mix the waste and soil completely. Initially, each plot was mowed and
raked to remove the existing vegetation. The plots were then rototilled
to an average depth of about 15 cm to facilitate subsequent waste
incorporation. Before application, the oily waste was thoroughly mixed to
assure uniformity. The waste was applied to the plots by a hand-held
sprayer in as uniform a manner as possible.
A split application approach was used. The total quantity of waste
applied to each plot was divided into three equal parts. Following each
waste application, the plots were rototilled immediately. Thus, each plot
was rototilled three times during the application of the waste.
In addition, each plot was rototilled after completion of the waste
application, process. At this time, the plots were rototilled twice in
perpendicular directions. The plots received no further tilling for the
duration of the study.
Spatial Variation
Shortly after the oily waste was applied to four of the plots and the
plots were rototilled in June 1983, ten random samples were taken from the
zone of incorporation (ZOI) of two of the plots that received the very
high waste applications. Each sample was analyzed for oil and grease,
volatile material, total Kjeldahl nitrogen, and pH. Ten random samples
also were taken from the same plots in November 1983. The second set of
samples helped identify the effects of time and degradative processes on
the spatial variation. The November samples were analyzed for the four
parameters noted above and for moisture content.
Each soil sample was kept separate and was prepared for analysis in
the following manner. First, each sample was mixed and hand sorted to
remove stones and large vegetative material. After subsamples were taken
89
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for moisture and pH determinations, the remaining soil was air dried at
room temperature (about 20°C). When air dry, the samples were pulverized
and passed through a No. 16 U.S. Standard Sieve which had a mesh opening
of 1.19 mm. The screened samples were then stored in screw-cap bottles at
room temperatures until analyzed.
The results of the June and November 1983 analyses are summarized in
Tables C-l and C-2. There were substantial variations in soil character-
istics, particularly in oil and grease, among each set of samples even
though every effort had been made to obtain the most uniform soil-waste
mixture possible.
Figure C-l illustrates the typical distribution of the parameters in
the subplot samples. Such distributions were similar for both sets of
subplot soil samples.
In each set, there were substantial differences among subplot samples
for all of the parameters considered with the exception of pH (Tables C-L
and C-2). The observed differences could be due to either spatial vari-
ation or random analytical error. To separate these factors, the analy-
tical results from each set of 10 subplot samples, two replicates per
sample for each parameter, were compared statistically.
The comparisons were made using a one way analysis of variance (8) to
test the null hypothesis that the subplot means for each parameter do not
differ significantly. The results of the comparison (Table C-3) indicated
that the observed differences within each set of subplots were statisti-
cally significant (P<0.05), and were due to spatial variation and not
random error.
The observed differences in mean values for oil and grease, total
Kjeldahl nitrogen, and volatile material between plots and between
sampling dates for each plot also were tested for statistical signifi-
cance. These comparisons were made using one-way analysis of variance (8)
followed by Duncan's new multiple range test (9) to analyze differences
between means.
The results of these statistical analyses are summarized in
Table C-4. Oil and grease concentrations in the two plots were not signi-
ficantly different (P<0.05) in either June or November. However, the oil
and grease concentrations were significantly different between June and
November indicating that reductions did occur in both plots between those
months.
There were significant differences between plots in total Kjeldahl
nitrogen and volatile material concentrations in both June and November
but no significant changes occurred in either plot with time. Although
significant reductions in oil and grease occurred in both plots between
June and November, the spatial variation as indicated by the coefficient
of variation for each plot (Tables C-l and C-2) remained essentially
constant.
90
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TABLE C-l. SUMMARY OF THE SOIL ANALYSIS - JUNE 1983.
vO
Oil and Volatile
Grease Material
(g/kg MFS*) (% MFS*)
Plot I Range 48.1 - 75.0 12.1 - 14.2
X ± SDt 62.0 ± 7.1 13.1 t 0.6
CV, %1 11.4 4.6
Cllt 56.9 - 67.1 12.7 - 13.5
Plot II Range 47.3 - 68.9 14.2 - 17.6
X ± SDt 57.0 ± 7.2 16.2 ± 1.2
CV, % 12.6 7.4
CI 51.8 - 62.2 15.3 - 17.1
Total Kjeldahl
Nitrogen
(g/kg MFS*) pll
2.04 - 2.88 6.7 - 6.8
2.56 ± 0.25 6.7 ± 0.1
9.8
2.38 - 2.74
3.27 - 3.99 6.7 - 6.9
3.62 ± 0.26 6.8 ± 0.1
7.2
3.43 - 3.81
*MFS = Moisture-free soil.
tic ± SD = Mean ± standard deviation, 11 = 10.
1CV, % = Coefficient of variance, percent.
- 95% confidence interval estimate:, to. 05'
-------
TABLE C-2. SUMMARY OF THE SOIL ANALYSIS - NOVEMBER 1983.
vO
to
Oil and Volatile Total Kjerldahl Moisture
Grease Material Nitrogen Content
(g/kg MFS*) (% MFS*) (g/kg MFS*) pH (%WBt)
Plot I Range
X ± SDt
CV, %//
CI§
Plot II Range
X t SD
CV, %
CI
31.1 - 50.8 11.8 - 14.2 2.48 - 2.86 6.9 28.0 - 32.8
43.3 ± 5.6 13.1 t 0.7 2.71 ± 0.13 6.9 31.0 ± 1.5
12.9 5.3 4.8 — 4.8
39.3 - 47.3 12.6 - 13.6 2.62 - 2.80 — 29.9 - 32.1
36.1 - 64.6 14.3 - 18.4 3.37 - 4.00 6.9 - 7.0 22.6 - 34.1
48.7 t 7.8 16.1 ± 1.2 3.67 ± 0.22 7.0 28.4 ± 3.9
16.0 7.4 (..0 — 13.7
43.1 - 54.3 15.2 - 17.0 3.51 - 3.83 — 25.6 - 31.2
*MFS = Moisture-free soil.
TUB = Wet basis.
IX ± SD = Mean ± standard deviation, n - 10.
//CV, % = Coefficient of variance, percent.
§CI = 95% confidence interval estimate, t0.o5-
-------
75
"5
c 70
I 85
JO
"o
60
o>
9
m 55
M
S 50
4
mt
® 45
1
•
»
^•^•^
_
1
'I
II. cOUZMOOZQ
SUBPLOT
FIGURE C-l
DISTRIBUTION OF OIL AND GREASE IN THE SOIL OF PLOT I, JUNE 1983
93
Reproduced (rorn
best available copy.
-------
TABLE C-3. RESULTS OF ANALYSES OF VARIANCE* FOR DIFFERENCES
AMONG SUBPLOTS.
Oil and
Grease
Variance Ratio (F)
Total Kjeldahl
Nitrogen
Volatile
Material
June 1983
Plot I
Plot II
27.84
44.74
26.16
9.54
6.40
21.24
November 1983
Plot I
Plot II
140.58
153.34
4.93
12.45
28.90
126.95
*Subplots differ significantly (P<0.05) if F>3.13.
TABLE C-4. RESULTS OF ONE-WAY ANALYSES OF VARIANCE TO EVALUATE
DIFFERENCES BETWEEN PLOTS AND BETWEEN SAMPLING DATES
FOR EACH PLOT - MEAN VALUES.
Oil and
Grease
(mg/g MFS*)
Total Kjeldahl
Nitrogen,
(mg/g MFS)
Volatile
Material
(% MFS)
June 1983
Plot I
Plot II
T
62.0 a
57.0 a
2.56 c
3.62 d
13.1 e
16.2 f
November 1983
Plot I
Plot II
43.3 b
48.7 b
2.71 c
3.67 d
13.1 e
16.1 f
*MFS - Moisture-free soil.
tMeans in the same column with a common letter are not significantly
different (P<0.05) (n=10).
94
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The differences noted In Table C-4 for the specific parameters can be
explained in terms of the amount of material that was added to the soil at
each plot and by the natural variations between plots. Table C-5 identi-
fies the background characteristics as determined from control plots.
TABLE C-5. OILY WASTE LAND TREATMENT SITE - BACKGROUND SOIL
CHARACTERISTICS* (DATA FROM CONTROL PLOTS).
Date
6/7/83
10/25/83
Oil &
Grease
(g/kg MFS)
0.6 4- 0.2
0.5 + 0.1
Volatile
Material
(% MFS)
8.8 + 1.5
9.4 + 1.5
TKN
(g/kg MFS)
3.3 + 0.7
3.5 + 0.8
PH
5.8 _+ 0.3
5.8 _+ 0.3
*n=4.
As a result of the waste application, the oil and grease and volatile
material concentrations in the ZOI (Tables C-l and C-2) were considerably
greater than the background (Table C-5). In contrast, the nitrogen addi-
tions were small, compared to the amount in the control plot soils, and
did not increase the ZOI concentrations measurably.
The results demonstrated that the spatial variation in industrial
waste and treatment site ZOI characteristics can be statistically signifi-
cant even when efforts are taken to insure uniform waste distribution and
incorporation. The coefficient of variation of the oil and grease concen-
trations ranged from 11.4 to 16%, of the volatile material concentrations
ranged from 4.6 to 7.4%, of the TKN concentrations ranged from 4.8 to 9.8%
and of the moisture content concentrations ranged from 4.8 to 13.7%
(Tables C-l and C-2). At an actual land treatment site, where less care
to obtain uniform distribution and mixing may be exerted, the coefficient
of variation may be greater.
The spatial variation at a land treatment site is a function of site
specific factors such as soil characteristics and methods of waste appli-
cation and incorporation. Determination of specific site spatial varia-
tion is desirable as a prerequisite for identifying sampling requirements.
The data help determine the number of random samples needed to obtain
a statistically significant estimate. Assuming that there will be random
sampling from a large number of possible subplots within a land treatment
site, the number of samples requijred to provide a desired level of
confidence that the sample mean (X) does differ from the average ZOI
characteristics by more than an identified acceptable error can be calcu-
lated using the following relationship (8).
95
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n = Z2S2/L2 (1)
Where n = the required number of samples
Z = the normal deviate
S2 = the population variance
L = the acceptable error
To use this relationship, it is first necessary to decide how accu-
rate the sample estimate should be, i.e., to identify the limits of error
(±L) that are acceptable. The required sample size is inversely propor-
tional to the square of the acceptable error. The number of samples
should provide an estimate that is useful, but the number should not be so
large that the cost of sampling and analysis is excessive. The reason for
obtaining the estimate of average site characteristics and the use of the
results should be clearly identified before deciding how accurate the sam-
ple estimate should be.
If it is desired to express the acceptable error as a percentage of
the sample mean, such as 30 rag/g i 10%, the expected sample mean must be
estimated before the required sample size can be calculated. The allow-
able error is then a function of the expected mean value and the required
sample size and the accuracy of the estimate increases .as the expected
mean value decreases.
It can not be guaranteed that the sample mean (X) will fall within
the limits of acceptable error (±L) since the normal distribution curve
extends from minus infinity to plus infinity. However, the probability
that this will occur can be specified. Assuming that a 5% chance that the
acceptable error (L) will be exceeded is acceptable, the value of the nor-
mal deviate (Z) is 1.96. For a 1% chance, the value of Z is 2.58. Values
of Z for other probabilities can be obtained from appropriate statistical
tables.
Finally, an estimate of the population variance (the standard devia-
tion squared) is needed. It can be necessary to rely on previous experi-
ence or results from similar industrial waste land treatment sites as the
basis for the estimate. If such information is not available, an educated
guess may be necessary.
The results of this study indicate that spatial variations in ZOI
characteristics vary little with time after waste is applied (Tables C-L
and G-2). Thus, the results from an initial estimate of average site
characteristics should permit a more precise determination of sampling
requirements for subsequent estimates.
An example can indicate how the number of samples can be determined.
Using data from Plot I, June 1983 (Table 8), Table C-6 identifies the
96
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number of samples that are needed for different levels of acceptable error
(±L) and different- probabilities that these limits will be exceeded. A
large number of samples is required for a small acceptable error and for
small probabilities that the limits will be exceeded.
TABLE C-6. ILLUSTRATION OF THE NUMBER OF RANDOM SAMPLES REQUIRED
FOR VARIOUS LEVELS OF ACCEPTABLE ERROR AND PROBABILITY.
Number of Samples
Parameter
Acceptable
Error
%*
Probability Error will be Exceeded
10%
**
5%
**
1%
**
Oil & Grease
(62.0 ± 7.1)t
Total Kjeldahl
Nitrogen
(2.56 ± 0.25)t
Volatile Material
(13.1 ± 0.6)t
20
10
5
20
10
5
20
10
5
1
4
14
1
3
11
1
1
3
2
5
20
1
4
15
1
1
4
3
9
35
2
7
26
I
2
6
^Percentage of sample mean that is the acceptable error.
^Probability that the acceptable error will be exceeded.
tMean ± standard deviation for Plot I, June 1983 (Table C-l).
The data in Table C-6 provide an estimate of the error associated
with samples taken from each of the plots to determine the changes in the
characteristics of the plots during this study.
97
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APPENDIX D
ANALYTICAL METHOD FOR THE DETERMINATION
OF OIL AND GREASE IN SOIL SAMPLES
Introduction
This study was undertaken to determine the precision and accuracy of
this method when used with soil samples. This information was of parti-
cular interest because oil and grease data were key analytical parameters
in this study.
Analytical methods for oil and grease are based on the fact that oil
and grease are insoluble in water, but are soluble in organic solvents.
Usually, the sample is acidified to convert soaps to fatty acids before
the oil and grease is extracted. In the determination of oil and grease,
an absolute quantity of a specific substance is not measured. Rather,
groups of substances with similar physical characteristics are determined
quantitatively on the basis of their common solubility in the solvent that
is used. Unlike some elements or compounds, oils and greases are defined
by the method used for their determination.
The solvents that have been used to determine oil and grease include
petroleum ether, hexane, benzene, chloroform and metHanoi, or carbon
tetrachloride. The solvent now commonly used in the water pollution
control field is trichlorotrifluorethane (3). This solvent represents
less of a hazard in the laboratory than many of the solvents noted above
since trichlorotrifluoroethane is not flammable or explosive and has no
known toxic properties (10).
Because no standard method exists for determining the oil and grease
content of contaminated soils, the precision and accuracy of a modified
form of the Soxhlet extraction method for sludge samples (Method 503D)
(3), was evaluated to determine the use of this method for the oil and
grease content of contaminated soils.
The results obtained by this method are empirical, and duplicate
results can be obtained only by strict adherence to all details. The rate
and time of extraction in the Soxhlet apparatus must be exactly as
directed because of the varying solubilities of different materials. In
addition, the length of time required to evaporate the solvent and cool
the extracted material cannot be varied. There may be a gradual increase
in weight, presumably due to absorption of oxygen or a gradual loss of
weight due to volatilization (3). Compounds volatilized at or below the
98
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temperature of solvent evaporation will be lost during the evaporating
process (3).
Soil samples containing known amounts, about 5% on a dry weight
basis, of several types of oil were analyzed. For each oil-soil mixture,
eight samples were analyzed. Eight samples of the soil without the oils
were analyzed as blanks. In addition, a second series of five oil-soil
mixtures were analyzed. These mixtures contained one to five percent, on
a dry weight basis, of the oily waste applied to the field plots. For
each oil concentration, two samples were analyzed.
Each stock mixture of oil and soil was prepared by adding the amount
of oil, or oily waste, on a weight basis, needed to produce the desired
concentration of oil or oily waste in 300 g of soil. After thorough mix-
ing, these stock mixtures were stored at room temperatures (20 to 22°C) in
screw-cap glass bottles until analyzed. When each oil-soil mixture was
prepared, the dry matter content of the soil was determined so that the
oil content of the stock mixtures could be expressed on a mg oil/g mois-
ture free soil basis. Coefficients of variation for dry matter determina-
tions never exceeded one percent.
The soil used for this study was from a site adjacent to the field
plots. To eliminate soil characteristics as a variable, all of the soil
used in this study was acquired at the beginning of the study and pro-
cessed in the following manner. First, the soil was hand sorted to remove
stones and vegetative matter. It then was mixed thoroughly for about 30
minutes using a portable concrete mixer and allowed to air dry at room
temperature (20°C) until it was friable. When dry, the soil was pulver-
ized and passed through a No. 16 U.S. Standard Sieve which had a mesh
opening of 1.19 mm and stored at room temperature in a closed container
until used.
The material used in this study were vegetable oil (partially hydro-
genated soy-bean oil), No. 2 fuel oil, No. 6 fuel oil, SAE 30 non-detergent
motor oil, and the oily waste used in the study.
Analytical Method
The method used in this study to determine the oil and grease content
of soils and oil-soil mixtures was a modified form of the oil and grease
extraction method for sludge samples (3). The following outlines the
steps that were followed.
1. About 15 g of the soil or oil-soil mixture to be analyzed was placed
in a preweighed, porcelain evaporating dish, 120 ml or larger, that
contained a glass stirring rod. The dish with the glass rod and the
soil was weighed again to determine.the weight of the added soil or
mixture.
2. Any soluble metallic soaps present were hydrolyzed by acidification
with concentrated hydrochloric acid to pH 2.0 or lower using pH test
paper as the method of measurement. To facilitate acidification,
99
-------
distilled water to produce a smooth paste-like mixture was added
before the acid.
3. After the acidified soil was mixed thoroughly with the stirring rod,
the soil was dried by adding MgSO^HjO that was prepared by drying
MgSOit-7H20 overnight at 150°C. Generally, 15-20 gm of MgSO^l^O was
sufficient.
4. The acidified soil and MgSOit-H20 were mixed using the stirring rod,
and then was placed in a desiccator and allowed to cool.
5. After weighing the dish with its contents and the stirring rod, the
contents of the dish were transferred to a porcelain mortar and
ground.
6. A subsample of the material from step 5, containing no more than 150
mg of oil, was placed in a tared cellulose extraction thimble and
weighed. The thimble was filled with small glass beads and placed in
a Soxhlet extraction tube.
7. Using a preweighed extraction flask that had been dried at L03°C and
cooled in a desiccator, the oil in the sample was extracted with 75
ml of reagent grade 1,1,2-tn.chloro-l,2,2-trifluoroethane for four
hours at a rate of 20 cycles/hour.
8. After extraction, the extraction flask was placed in a 70°C water
bath for one hour to evaporate the solvent. At the end of the hour,
air was drawn through the flask for one minute using a vacuum pump to
remove any remaining vapors.
9. Finally, the flask was weighed again after cooling in a desiccator
for 30 minutes to determine the weight of extracted oil and grease.
Although this procedure is almost identical to method 503D for sludge
samples outlined in (3), it differed in one important aspect. The Stan-
dard Methods procedure requires the quantitative transfer of the mixture
of acidified sample and HgSOit'HjO first Co A mortar for grinding and ;'.ien
to an extraction thimble. The procedure used in this study eliminated
possible errors associated with these transfers. It also permitted the
use of a larger, more representative original sample which is an advantage
when the oil and grease concentration limits the size of the sample that
can be extracted. The subsample extracted contained portions of the
original soil and the water and chemicals that were added.
The concentration of oil and grease in each soil sample was expressed
as mg oil and grease per gram moisture free soil. The calculations were
as follows:
Oil and grease (mg/g) _ extraction flask weight gain (mg) ,„.
moisture free soil soil extracted (g) x dry matter fraction
100
-------
where:
soil _ subsaraple soil sample (g) ,,>
extracted(g) extracted(g) soil sample + H20 + HC1 + MgS04-H20 (g)
Results
The results of this evaluation are summarized in Tables D-L, D-2 and
D-3. The precision (coefficient of variation) of this method was
excellent (Tables D-l and D-2). The accuracy (percent recovery) varied
with type of oil (Table D-3) and with the concentration of the oily waste
(Table 15).
Precision - As shown in Tables D-l and D-2, the coefficient of varia-
tion of the oil-soil mixtures analyzed never exceeded four percent. There
was little variation in precision as the concentration of oily waste
varied (Table D-2).
The reason for the observed variability in the results for the blank,
air dried soil samples is unclear, but it has been observed by the authors
in other investigations. The coefficient of variation (50%) is large only
in relative terms because the oil content of these samples was so low.
Routine analysis of the residue content of the reagent grade
trichlorotrifluoroethane used in this study indicated that solvent con-
tamination was not responsible for the observed variability. Residue
after evaporation never exceeded 0.1 mg/LOO ml.
Accuracy - The accuracy of this method varied with the oil type
(Table D-3). With the exception of motor oil, the quantities added were
underestimated.
The reasons for these differences in accuracy were not determined.
It is known that extraction efficiency varies with oil composition and
with the constituents being extracted. Only those substances that are
soluble in the solvent used for extraction can be determined
quantitatively (3).
The percent recovery for No. 2 fuel oil was the lowest among all of
the oils used in this study (Table D-3). It is possible that losses of
volatile constituents could have occurred during the preparation of the
stock oil-soil mixtures as well as during sample acidification and dry-
ing. McGill and Rowell (11) have reported recoveries of about 70 percent
for untopped crude oils (volatiles not removed) versus about 95 percent
recovery for crude oils that had been topped at 21°C for 3 days. The sol-
vent used was methylene chloride.
As shown in Table D-2, percent recovery increased as the concentra-
tion of oil in the oily waste-soil mixtures increased. Regression analy-
sis of the analytical results indicated that the magnitude of the
underestimate was constant. This indicates that the observed difference
101
-------
TABLE D-l. PRECISION OF SOXHLET EXTRACTION WITH TRICHLOROTRIFLUOROETHANE
TO MEASURE THE OIL AND GREASE CONTENT OF SOIL
mg oil/g MFS*
Oil
Blank//
Vegetable oil
Fuel oil, No. 2
Fuel oil, No. 6
Motor oil, SAE 30**
Oily waste
Range
0
41
33
41
50
47
.1 -
.1 -
.6 -
.9 -
.8 -
.0 -
0.3
45.8
35.1
45.0
57.1
53.1
X + SDt
0.2
43.2
34.5
43.9
54.7
50.2
± °-
+ 1.
± °-
+ 0.
± 2>
± 2-
1
6
6
9
2
0
CIf
0.1
42.0
34.0
43.1
52.9
48.5
- 0.
- 44
- 35
- 44
- 56
- 51
3
.6
.0
.7
.7
.9
CV
50
3
1
2
4
4
9 «
.0
.7
.7
.0
.0
.0
*MFS = moisture-free soil
TX + SD = mean +_ standard deviation, n = 8.
1CI = 95% confidence interval estimate,
§CV, % = coefficient of variance, percent.
//air-dried soil
**non-detergent oil
TABLE D-2. PRECISION AND ACCURACY AS FUNCTIONS OF CONCENTRATION:
FOR OILY WASTE-SOIL MIXTURES
mg oil/g
Stock Mixture
10.5
21.0
31.4
41.9
52.2
MFS*
Recovered
3.8 + O.lt
18.0 + 0.4
29.4 + 0.1
40.5 + 0.6
50.0 + 0.6
Coefficient of
Variance (%)
l.l
2.2
0.3
1.5
1.2
Recovered
(%)
83.8
85.7
93.6
96.7
95.8
*MFS = moisture-free soil
tblank corrected mean + standard deviation, n = 2.
102
-------
TABLE D-3. ACCURACY OF MEASURING THE OIL CONTENT OF SOIL —
SOXHLET EXTRACTION WITH TRICHLOROTRIFLUOROE-THANE
Oil
Blank//
Vegetable oil
Fuel oil, No. 2
Fuel oil, No. 6
Motor oil, SAE 30**
Oily waste
rag
Stock Mixture
0
50.6
50.7
52.9
53.5
52.2
oil/g MFS*
Recovered
0.2
43.0
34.3
43.7
54.5
50.0
± 0.1
± 1.6
± 0.6
± 0.9
± 2.2
± 2.0
Percent
Recovered
-
85.4
68.0
83.0
102.2
96.2
*MFS = moisture-free soil
T = blank corrected mean + standard deviation, n = 8.
If = air-dried soil
**non-detergent oil
TABLE D-4. SUMMARY OF RESULTS — MEASURING THE OIL CONTENT OF SOIL
USING SOXHLET EXTRACTION WITH TRICHLOROTRIFLUOROETHANE
Oil.
Blank*
Vegetable oil
Fuel oil, No. 2
Fuel oil, No. 6
Motor oil, SAE 30t
Oily waste
Coefficient of
Variation (%)
50.0
3.7
1.7
2.0
4.0
4.0
Percent
Recovered
-
85.4
68.0
83.0
102.2
96.2
*air-dried soil
tnon-detergent oil
103
-------
was not a function of concentration but of an unknown constant error. The
difference between the intercept of the regression line ^.(-2.24 rag oil and
grease/gram moisture free soil) and the origin was teste'd statistically
and was not found to be significant (t<0.05).
The results are summarized in Table D-4 and indicate that the modi-
fied method identified in this paper, which-consists of acidification fol-
lowed by Soxhlet extraction with trichlorotrifluoroethane, is precise and
results in reasonable recoveries when used to measure the oil and grease
content of contaminated soils.
104
-------
o
in
APPENDIX E
CATION EXCHANGE CAPACITY OF THE SOIL IN
THE FIELD PLOTS - 1982 to 1984 (n = 4)
TYPE OF
APPLICATION
Natural
Control
Rototllled
Control
Low
Medium
High
Very High*
June 4
1982**
25.2
± 8.5
25.0
± 7.8
25. A
± 3.0
24.8
± 2.9
28.7
± 7.5
-
June 21
1982
26.3
± 4.5
28.6
± 7.0
26.4
± 6.1
24.5
± 4.8
27.5
± 5.1
-
October 5
1982
24.9
± 3.6
25.3
± 4.6
25.3
± 2.9
24.6
± 2.3
26.1
± 4.8
-
November 9 June 21
1982 1983
23.9
± 3.8 -*
25.2
± 5.3
22.8
± 7.9
24.3
± 3.7
23.5
± 3.6
25.5
± 6.4
October 25
1983
24.8
± 4.7
-
-
-
26.6
± 4.8
25.1
± 5.8
April 26
1984
24.1
± 3.9
-
-
-
23. I
± 4.6
22.9
± 4.6
Symbol indicates that the parameter was not measured on the noted dates in the respective
plots.
+In June 1983, the low application plots became the very high application lots (see text
SECTION 5).
**
Background data before any wastes were applied or the plots were irototil led.
-------
TABLE F-l. SUMMARY OF AVERAGE DATA FOR THE NATURAL CONTROL PLOTS (n = A)
Sampling
Date
1982
June 4**
June 21
July 13
August 17
September 13
October 5
November 9
1983
March 14
May 5
June 6
June 23 •
July 6
August 3
September 13
October 25
1984
April 24
June 6
July 9
PH
5.9±0.1
5.6±0.1
5.6±0.1
5.7±0.2
5.410.1
5.6±0.1
5.410.1
5.810.2
5.8*0.2
5.510.1
-
5.410.2
5.610.1
5.810.1
5.810.2
5.810.2
5.610.2
5.510.2
Soil
Moisture
(% WB)
-*
29.8213.82
20.0413.06
23.4811.63
13.5913.09
23.18i2.23
26.55±1.99
29.5513.84
29.54±4.26
28.3511.59
-
21. 17H.98
18.4813.50
12. 37±1.83
24.1012.32
29.8214.85
27.4313.08
28.913.66
Volatile
Matter
(% Soil
MFB)
8.3011.20
9.1811.04
8.5711.43
8.6311.51
9.3611.30
9.1110.97
9.0411.17
10.2311.16
9.29+1.47
9.1310.93
-
8.8011.22
9.1711.28
8.9810.97
9.1611.37
8.8711.12
8.9611.02
8.9510.86
Oil .ind
Grease TKN
(g/kg MFB) (g/kg MFB)
3.1210.41
3.3010.56
3.2410.54
3.2310.52
3.2610.55
3.5410.55
3.3410.45
3.4510.49
3.3210.53
3.4510.39
-
3.3310.49
3.3410.35
3.3810.44
3.3810.57
3.3410.47
3.2910.40
3.1210.33 .
Soil
Temperature
(°C)
-
16.910.2
21.810.1
19.510.6
16.010.0
12.810.5
7.810.5
3.5+0.6
10.210.5
15.810.5
24.211.5
20.2+0.5
19.8*0.3
20.110.2
11. 110. 2
7.010.0
15.910.2
16.210.3
*Symbol means that the parameter was not measured on the noted dates.
**Background sample taken before any wastes were applied or the plots wete rototilled.
-------
TABLE F-2. SUMMARY OF AVERAGE DATA FOR THE ROTOTILLED CONTROL PLOTS (n = 4)
Sampling
Date
1982
June 4**
June 21
July 13
August 17
September 13
October 5
November 9
1983
March 14
May 5
June 6
June 23
July 6
August 3
September 13
October 25
1984
April 24
June 6
July 9
PH
5.8±0.1
5.6±0.1
5.7±0.2
5.7±0.2
5.8±0.2
5.810.2
5.8±0.2
5.910.4
5.810.6
5.810.3
-
5.810.4
5.810.3
5.710.3
5.810.3
5.810.2
5.810.2
5.610.4
Soil
Moisture
(% WB)
_*
31.1714.78
23.5014.59
25.7213.98
16.4016.08
23.2313.46
27.4415.24
31.0015.28
29.2415.10
25.2015.22
-
17.2713.67
15.7114.00
11.7614.12
24.4313.05
28.9814.84
27.3214.48
24.2515.81
Volatile
Matter
(% Soil
MFB)
9.1212.60
9.2011.72
8.4811.46
8.7311.21
9.5812.00
9.3511.28
9.1911.82
9.1611.33
9.15H.66
9.1211.38
-
9.1411.54
9.5811.69
9.4111.64
9.3611.44
8.7911.35
8.7511.02
9.1111.35
Oil and
Grease
(g/kg MFB)
-
-
-
-
-
0.2110.10
0.3310.20
0.2210.05
0.6810.16
0.6510.17
-
0.5910.24
0.4410.12
0.6810.19
0.5410.11
0.5710.12
-
0.3610.10
TUN
(g/kg MFB)
3.2510.63
-
-
3.3210.65
3.5510.88
3.5010.61
3.4910.84
3.4710.61
3.2510.92
3.3310.70
-
3.4910.76
3.5310.79
3.5410.79
3.3710.66
3.4910.62
3.2310.51
3.3010.61
Soil
Temperature
(°C)
-
16.010.4
22.510.6
19.8+0.5
16.010.8
13.010.0
8.010.8
3.510.6
10.210.5
17.011.8
23.010.0
20.410.5
20.110.2
20.010.7
11.110.2
7.010.0
16.511.0
16.410.6
*Symbol means that the parameter was not measured on the noted dates.
**Background sample taken before any wastes were applied or the plots were rototilled.
-------
TABLE F-3. SUMMARY OF AVKKAGE DATA FOR THE LOW APPLICATION PLOTS (n = 4)
o
GO
Sampling
Date
1982
June 4**
June 21
July 13
August 17
September 13
October 5
November 9
1983
March 14
May 10
June 6
PH
6.0±0.2
5.7±0.2
5.4±0.2
5.5±0.2
5.8±0.2
5.8±0.2
6.0±0.1
6.2±0.3
6.110.2
6.010.1
Soil
Moisture
(% WB)
_*
31.9614.77
23.3J13.52
24.2DH.82
16.3212.30
23.6911.45
27.4ail.83
29.7215.77
30.5313.19
26.0112.70
Volatile
Matter Oil and
(% Soil Grease
MFB) (g/kg MFB)
8.5611.36
9.4411.74
8.36H.13
8.8211.29
9.1611.35
9.2711.30 0.3910.15
10.4211.83 5.4811.08
10.0111.54 4.6010.91
10.3111.23 4.1810.46
10.3211.51 3.7910.73
TKN
(g/kg MFB)
-
-
-
3.2910.58
3.5110.64
3.5410.62
3.7110.84
3.5010.65
3.5410.62
3.5810.68
Soil
Temperature
(°C)
-
16.110.2
22.8±0.5
19.810.5
15.810.5
12.510.6
8.010.8
3.211.0
10.010.8
16.510.6
*Symbol indicates that the parameter was not measured on the noted dates.
**Background sample taken before any wastes were applied or the plots were rototilled.
-------
TABLE F-4. SUMMARY OF AVEKAGE DATA FOR THE MEDIUM APPLICATION PLOTS (n = 4)
Sampling
Date
1982
June 4**
June 21
July 13
August 17
September 13
October 5
November 9
1983
March 14
May 5
June 6
June 23
July 6
August 3
September 13
October 25
1984
April 24
June 6
July 9
PH
5.9±0.2
5.5±0.2
5.5+0.2
5.4±0.3
5.8±0.2
5.8±0.2
6.0±0.2
6.3±0.2
6.2±0.1
6.2±0.3
-
6.3±0.1
6.1±0.1
6.U0.1
6.210.1
6.2+0.1
6.1±0.1
6.210.1
Soil
Moisture
(z WB)
_*
30.3814.86
23.80±2.80
24.7112.12
14.94±2.86
22.7611.12
27.0011.84
31.0414.85
28.28il.45
26.4911.47
-
19.6511.59
18.78H.74
12.7612.13
25.1911.97
29.0612.90
27.8913.21
29.2614.87
Volatile
Matter
(% Soil
MFB)
8.2211.17
8.9011.02
8.4410.98
8.6810.88
9.0610.96
8.8610.74
10.4111.60
10.0011.53
10.2611.15
10.4910.78
-
10.1611.15
9.9211.22
10.2711.44
10.3211.07
9.3210.56
10.0210.94
9.2210.56
Oil and
Grease
(g/kg MFB)
-
0 . 94 J 0 . 1 I
-
-
0.5410.17
0.6610.09
9.3U2.92
8.6412.93
8.8211.58
9.2412.24
-
7. 30 J 1.78
6.88H.04
7.0411.94
6.0110.47
4.9811.25
5.0110.38
4.3711.08
TKN
(g/kg MFB)
-
3.2010.56
-
3.0810.48
3.4010.51
3.4710.49
3.3010.66
3.3610.65
3.2810.41
3.2210.42
-
3.4410.64
3.4410.66
3.5010.59
3.4110.55
3.2810.34
3.4010.48
3.1710.34
Soil
Temperature
(°C)
-
16.010.0
22.810.5
19.810.5
16.010.0
13.010.0
8.210.5
3.510.6
10.211.0
16.510.6
24.810.5
21.410.5
19.910.2
20.210.3
11. 010.0
7.210.3
16.211.0
16.910.2
*Symbol indicates that tlie parameter was not measured on Llie noted dates.
**Background sample taken before any wastes were applied or the plots were rototilled.
-------
TABLE F-5. SUMMARY OF AVERAGE DATA FOR THE HIGH APPLICATION PLOTS (n = 4)
Sampling
Date
1982
June 4**
June 21
July 13
August 17
September 13
October 5
November 9
1983
March 14
May 5
June 6
June 23
July 6
August 3
September 13
October 25
1984
April 24
June 6
July 9
PH
5.810.2
5.610.2
5.710.1
5.810.2
5.810.2
5.910.2
6.210.2
6.410.1
6.410.1
6.210.1
-
6.510.1
6.510.2
6.410.1
6.410.1
6.410.1
6.210.1
6.510.1
Soil
Moisture
(% WB)
_*
30.1014.31
25.6812.24
26.7913.25
17.1014.84
24.1113.54
26.9013.28
30.0114.55
31.7717.30
27.2013.32
-
22.1311.99
20.3712.98
14.5812.44
25.7612.89
29.3614.20
27.7713.18
27.8814.70
Volatile
Matter
(% Soil
MFB)
8.8311.34
9.2111.33
8.9811.06
9.3311.59
10.3711.24
9.9411.35
11.8011.81
11.7411.50
11.7411.69
11.2011.50
-
11.5111.44
11.1411.47
11.8911.13
11.1311.78
11.2611.15
10.4411.06
10.8711.18
Oil and
Crease
(g/kg MFB)
-
1.9810.38
1.0810.28
1.0810.31
1.12±0.24
1.2010.27
19.6012.83
17.9015.12
14. 8616. 40
14.8613.17
-
15.99H.20
10.8311.85
13.4212.29
9.4012.35
10.3512.16
7.7812.34
6.4410.98
TKN
(g/kg MFB)
•
3.1410.57
3.4210.54
-
3.0810.50
3.7210.57
3.7410.59
3.5410.55
3.6010.49
3.6110.81
3.5010.47
-
3.6210.52
3.4210.67
3.7310.53
3.3410.54
3.6510.49
3.4410.44
3.5010.56
Soil
Temperature
-
16.110.6
22.810.5
19.810.5
16.210.5
13.510.6
8.210.5
3.2H.O
10.010.0
17.011.4
24.510.6
22.010.0
20.510.7
20.010.0
11.410.2
.* 7.010.0
16.510.6
16.910.8
*Symbol indicates that the parameter was not measured on Die notod dates.
**Background sample taken before any wastes were applied or Llie plots were rototilled.
-------
TABLE F-6. SUMMARY OF AVERAGE DATA FOR THE VERY HIGH APPLICATION PLOTS (n = 4)
Sampling
Date
1983
June 23
July 6
August 3
September 13
October 25
1984
April 24
June 6
July 9
PH
7.U0.2
6.9±0.1
6.8+0.0
6.7±0.1
6.8±0.1
6.7±0.1
6.8+0.0
6.7+0.1
Soil
Moisture
(% UB)
22.64±1.92
20. 26+1.59
19.4613.09
20.96±2.00
28.56+1.92
31.94±3.94
31.56il.84
30.92+1.21
Volatile
Matter
(% Soil
MFB)
14.98±1.33
14.24+1.97
15.28+1.75
14.20+1.34
13.86+1.36
13.90+1.64
13.56±1.22
12.67+1.73
Oil and
Grease
(g/kg MFB)
56.16±2.09
55.85±6.52
51.10±2.59
37.86+4.93
34.22±1.12
31.63+3.73
31.72±2.46
28.63+3.58
TKN
(g/kg MFB)
3.24+0.66
3.22±0.61
3.42±0.52
3.61±0.62
3. 31 ±0.66
3.5610.66
3.45±0.62
3.50±0.65
Soil
Temperature
(°C)
26.2+0.5
25.6+1.1
24.U1.6
22.9+0.2
12.410.9
7.310.3
19.6+1.8
19.1+0.6
-------
TABLE G-l
METAL CONCENTRATIONS* IN THE SOILS OF NATURAL CONTROL PLOTS
(rag/kg MOISTURE FREE SOIL) (n = 4)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
00
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
27 , 200
±2,300
<**
3,200
±720
31
±3
14
±3
26,700
±2,000
<
4,800
±290
650
±210
27
±2
3,700
±630
220
±57
160
±48
43
±4
98
±13
6/21/82
25 , 300
±2,400
<
3,300
±700
29
±3
14
±3
26 , 300
±2,300
<
4,800
±330
590
±140
26
±3
3,100
±650
190
±J4
110
±14
38
±4
99
±14
10/5/82
22,800
±1,700
<
3,200
±800
26
±2
16
±4
27,000
±3,000
24
±4
4,400
±370
540
±200
24
±4
1,900
±350
470
±t>0
53
±25
32
±3
93
±11
11/9/82
23,700
±4,000
<
3,200
±700
29
±5
17
±4
27 , 300
±2,900
25
±3
4,500
±350
570
±200
26
±3
2,000
±700
420
±35
74
±36
37
±7
99
±15
6/6/83
26 , 000
±3,900
<
3,300
±710
30
±4
16
±3
28,000
±2 , 300
25
±1
4,600
±330
580
±86
25
±2
3,000
±830
120
±23
100
±25
40
±6
98
±15
10/25/83
23,900
±2,500
<
3,200
±800
27
±3
16
-^4
27,000
±2 , 300
19
±2
4,400
±360
530
±140
25
±3
2,400
±660
78
±21
61
±21
36
±5
92
±11
6/6/84
26 , 300
±2,400
<
3,400
±700
30
±3
15
±3
27,400
±2,500
25
±8
4,500
±360
600
±140
26
±3
3,000
±700
<
86
±29
40
±4
105
±17
+ Average and standard deviation of the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
**< = less than the limit of detection determined by instrument
sensitivity, sample dilution, and matrix interference.
112
-------
TABLE G-2
METAL CONCENTRATIONS* IN THE SOILS OF ROTOTILLED CONTROL PLOTS
(mg/kg MOISTURE FREE SOIL)(n = 4)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
27,900
±3,000
<**
3,400
±1,000
31
±3
15
±3
27,500
±2,900
<
4,800
±280
630
±220
26
±2
3,500
±820
210
£47
130
±24
41
±5
98
±14
6/21/82
27 , 200
±3,900
<
3,500
±1,100
30
±5
15
±3
26,700
±1,800
<
4,800
±380
600
±230
27
±3
3,800
±l,LOO
230
±36
120
±30
40
±7
98
±12
10/5/82
22,200
±3,400
<
3,500
±1,100
27
±4
18
±3
27 , 700
±2,900
23
±3
4,300
±520
600
±280
24
±4
1,700
±690
460
£190
27
±11
31
±5
93
±13
11/9/82
21,400
±1,700
<
3,500
±1,200
25
±6
20
±4
26,400
±2,300
25
±2
4,200
±380
580
±240
25
±2
1,600
±240
330
£80
64
±28
34
±3
96
±17
6/6/83
28,000
±4,400
<
3,500
±1,000
31
±5
18
r4
28,000
±2 , 500
24
±2
4,800
±440
560
±190
25
±3
3,600
±1 , 100
140
i43
130
±38
43
±7
98
±15
10/25/83
24,000
±860
<
3,400
±1,000
27
±1
15
±3
27,000
±2,000
19
±2
4,400
±240
570
±250
24
±3
2,300
±330
83
i4
64
±24
36
±2
88
±10
6/6/84
25,800
±3,700
<
3,500
±1,100
29
±4
15
±3
27 , 100
±2,800
22
±2
4,480
±460
600
±270
25
±3
2,800
±890
40
16
75
±18
39
±6
95
±22
+ Average and standard deviation of the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
**<= less than the limit of detection determined by instrument
sensitivity, sample dilution, and matrix interference.
113
-------
TABLE G-3
METAL CONCENTRATIONS"*" IN THE SOIL OF THE LOW
APPLICATION PLOTS (rag/kg MOISTURE FREE SOIL)(n
4)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
GO
Sodium
(Ma)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
25 , 800
±2,700
<**
3,300
±650
29
±3
14
±2
26 , 300
±2,600
<
4,700
±400
610
±100
26
±2
3,200
±860
210
±46
120
±15
38
±4
100
±5
6/21/82
27,000
±2,800
<
3,500
±780
32
±3
15
26,000
±3,000
27
±2
4,800
±430
650
±120
26
±3
3,800
±850
220
±46
120
±15
40
±4
105
±11
10/5/82
23,700
±2,500
<
3,450
±700
29
±2
17
26,700
±1,700
23
±2
4,300
±250
530
±60
24
±2
2,300
±550
530
±130
52
±27
34
±3
100
±13
11/9/82
25,000
±2,400
<
4,800
±1,000
48
±4
21
±3
26,200
±3,000
31
±3
4,400
±420
560
±100
25
±3
2,500
±750
440
±25
97
±22
40
±3
130
±13
6/6/83
25,000
±11,000
<
3,800
±1,800
41
±18
15
±7
22,000
±9,300
24
±9
3,900
±1,700
440
±180
20
±9
3,600
±1,500
150
±60
140
±55
38
±16
110
±51
+ Average and standard deviation of the data from
the four plots on the noted sampling data.
* Background sample taken before any wastes were
applied or the plots were rototilled.
**< = less than the limit of detection determined
by instrument sensitivity, sample dilution, and
matrix interference.
114
-------
TABLE G-4
METAL CONCENTRATIONS* IN THE SOIL OF MEDIUM APPLICATION PLOTS
(mg/kg MOISTURE FREE SOIL)(n = 4)
Sampling Date
Mecal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
26,900
±3,000
<**
3,300
±770
30
±3
15
±2.9
25,900
±1,900
<
4,700
±360
570
±130
25
±3
3,700
±970
220
±50
135
±11
41
±4
96
±7
6/21/82
26,100
±890
<
3,600
±620
33
±1
14
±2.2
25,700
±1,600
<
4,700
±220
570
±140
26
±2
3,400
±400
210
±30
120
±19
38
±2
104
±7
10/5/82
22,000
±2,000
<
3,300
±660
29
±2
17
±0.9
25 , 500
±1,000
24
±2
4,100
±160
500
±120
22
±2
1,900
±430
500
±100
58
±7
32
±3
94
±10
11/9/82
25,600
±1,800
<
5,000
±1,200
51
±8
21
±3.3
26,600
±2 , 500
32
±4
4,500
±400
530
±110
26
±3
2,700
±810
430
±38
100
±10
40
±3
140
±19
6/6/83
31,000
±2,900
<
5,600
±520
62
±4
21
±1.2
27,000
±1,600
30
±1
4,800
±310
530
±110
25
±2
4,900
±1,000
220
±55
L60
±44
47
±5
160
±7
10/25/83
26,300
±3,100
<
4,500
±1,800
43
±20
17
±4.6
26,400
±2,000
22
±5
4,400
±370
520
±140
24
±3
3,200
±L,400
130
±59
94
±53
40
±6
120
±40
6/6/84
31,000
±2,400
<
5,400
±860
57
±5
19
±2.5
27 , 300
±3,000
27
±2
4,700
±400
620
±190
26
±3
4,700
±1,000
64
±31
140
±21
48
±4
150
±15
+ Average and standard deviation of. the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
**< = less than the limit of detection determined by instrument
sensitivity, sample dilution, and matrix interference.
115
-------
TABLE G-5
METAL CONCENTRATIONS'1" IN THE SOIL OF HIGH APPLICATION PLOTS
(mg/kg MOISTURE FREE SOIL)(n = 4)
Sampling Dace
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
26,900
±2,300
<**
3,600
±1,000
31
±4
16
±3
27,500
±2,500
<
4,900
±390
700
±210
27
±2
3,400
±860
200
r41
140
±50
42
±6
100
±15
6/21/82
29,400
±2,300
<
4,100
±700
39
±5
16
±2
26,900
±2,100
<
4,900
±320
600
±170
27
±3
4,100
±640
240
±17
150
±26
44
±4
120
±19
10/5/82
23,200
±3,600
<
3,900
±860
33
±4
18
±4
26,200
±2,700
25
±4
4,300
±600
660
±230
24
±4
2,100
±1,000
500
sl30
66
±33
34
±6
100
±12
11/9/82
27 , 200
±2,600
<
5,800
±740
63
±8
24
±1
27 , 300
±1,100
42
±15
4,500
±330
650
±190
26
±2
3,100
±910
600
±140
120
±47
44
±5
160
±26
6/6/83
36,000
±3,100
<
7,100
±990
79
±1
25
±3
27,000
±1,900
34
±2
5,100
±350
640
±140
26
±2
7,000
±1,200
. 300
t32
240
±43
56
±5
200
±25
10/25/83
26,800
±2,900
<
4,000
±1,300
36
±11
18
±4
27 , 300
±1,700
22
±4
4,500
±340
660
±190
26
±3
3,000
±920
120
±28
96
±31
42
±6
110
±32
6/6/84
31,900
±5,000
<
6,400
±1,030
68
±12
22
=4
27,400
±2,400
30
±3
4,800
±510
630
±190
26
±3
5,000
±1,900
67
±55
140
±59
49
±9
180
±30
+ Average and standard deviation of. the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
**< = less than the limit of detection determined by instrument
sensitivity, sample dilution, and matrix interference.
116
-------
TABLE G-6
METAL CONCENTRATIONS* IN THE SOIL OF THE VERY HIGH
APPLICATION PLOTS (mg/kg MOISTURE FREE SOIL)(n = 4)
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cd)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
"(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/21/83
32,200
±2,500
<
13,200
±960
145
±10
43
±3
24,000
±1,600
53
±3
4,600
±330
520
±76
23
±3
6,000
±770
370
±43
220
±16
50
±4
340
±19
Sampling Date
10/25/83
32 , 200
±3,400
<*
12,400
±3,800
140
±40
35
±9
25,200
±1,800
48
±12
4,600
±360
500
±39
25
±2
5,700
±1,300
310
±b2
200
r52
50
±6
320
±89
6/6/84
35,200
±4,300
<
13,700
±1,100
160
±11
38
±4
25,500
±3,000
54
±3
4,800
±520
520
±75
26
±3
7,400
±1,800
210
:68
220
±40
55
±7
380
±22
+ Average and standard deviation of the data from
the four plots on the noted'sampling data.
* < = less than the limit of detection determined by
instrument sensitivity, sample dilution, and
matrix interference.
117
-------
TABLE H-l
ORGANIC CONCENTRATIONS IN THE SOILS OF PLOT 5 - A VERY HIGH APPLICATION
PLOT (rag/kg MOISTURE FREE SOIL)*
Sampling Date
Organic Compound
6/23/83 7/6/83 8/3/83 9/14/83 10/25/83
Napthalene
2-methyl-napChalene
1-methyl-napthalene
2 , 6-dimethyl-napthalene
1 , 3-dimethyl-napthalene
2 , 3-dimethyl-napthalene
1 , 2-dimethyl-napthalene
Cg Alkane
Cg Alkane
GIO Alkane
C ! i Alkane
C12 Alkane
C13 Alkane
Cm Alkane
GIS Alkane
Cjg Alkane
C17 Alkane
C18 Alkane
C19 Alkane
C2o Alkane
C21 Alkane
C22 Alkane
C23 Alkane
C2i» Alkane
C2s Alkane
C2g Alkane
Biphenyl
3-raethyl-biphenyL
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
1-methylphenanthrene
Pyrene
25
45
74
329
491
159
91
<10*
<10
21
55
91
127
203
193
265
235
216
199
172
118
79
61
55
129
44
32
64
66
16
33
17
<10
42
37
<9* <10* <10*
21
13
46
41
57
61
<10
<10
<10
<10
16
29
54
104 " 9
122 " <7*
134 " 9
140 6 14
156 10 11
156 8 13
108 <10 <10
72
46
48
59
38
<10
it ii ii
" " "
.. .• ii
•• •• ii
•• n ii
•i ii n
•• n n
26 20 10
<10*
fi
ti
*•
11
11
'•
"
• i
"
M
••
"
11
"
11
11
11
"
11
it
M
••
"
""
"
"
**
••
••
"
*•
••
11
6
+ the very high waste application occurred on June 19,1983.
* less than the noted detection limit of the analytical methods when
calculated in terms of these units.
118
-------
TABLE H-2
ORGANIC CONCENTRATIONS IN THE SOILS OF PLOT 12 - A VERY HIGH APPLICATION
PLOT (rag/kg MOISTURE FREE SOIL)+
Sampling Date
Organic Compound
6/23/83 7/6/83 8/3/83 9/14/83 10/25/83
Napthalene
2-methyl-napthalene
1-methyl-napthalene
2 , 6-dimethyl-napthalene
1 , 3-dimethyl-napthalene
2 , 3-dimethyl-napthalene
1 ,2-dimethyl-napthalene
C8 Alkane
Cg Alkane
CIQ Alkane
C i i Alkane
C}2 Alkane
C i 3 Alkane
C14 Alkane
C15 Alkane
Cxe Alkane
C}7 Alkane
CIQ Alkane
C19 Alkane
C£Q Alkane
C2i Alkane
€22 Alkane
C23 Alkane
024 Alkane
C25 Alkane
C2e Alkane
Biphenyl
3-methyl-biphenyl
Dibenzof uran
Fluorene
Phenanthrene
Anthracene
Carbazole
1-methylphenanthrene
Pyrene
22
37
36
257
382
123
62
<10*
<10
24
54
99
185
276
386
341
402
377
344
295
188
135
98
84
160
44
31
61
66
22
23
16
<10
51
25
<10*
17
<10
<10
23
24
<10
"
"
M
"
11
44
87
123
77
110
112
120
126
80
58
54
52
114
66
24
10
23
23
<10
••
••
13
20
<10*
11
M
"
11
*'
II
"
"
11
11
11
"
10
26
17
25
26
23
35
17
14
22
14
41
17
<10
"
ii
•*
11
11
"
it
<10*
11
11
"
11
ii
"
ii
"
11
11
"
11
"
13
23
19
23
18
25
16
<10
ii
11
16
<10
11
ii
"
"
11
•*
ii
11
<10*
"
11
41
"
"
11
'*
"
11
"
11
"
"
"
**
15
<10
••
**
ii
••
"
11
31
<10
*"
"*
*'
"
"
"
"
"
+ the very high waste application occurred on June 19,1983.
* less than the noted detection limit of the analytical methods when
calculated in terms of these units.
119
-------
TABLE H-3
ORGANIC CONCENTRATIONS IN THE SOILS OF PLOT 18 - A VERY HIGH APPLICATION
PLOT (mg/kg MOISTURE FREE SOIL)+
Organic Compound
Sampling Date
7/6/83
10/25/83
6/6/84
C9
Napthalene
2-methyl-napthalene
1-methyl-napthalene
2,6-dimethyl-napthalene
1,3-dimethyl-napthalene
2,3-dimethyl-napthalene
1,2-dimethyl-napthalene
C8 Alkane
Alkane
Alkane
Cu Alkane
C12 Alkane
Cj3 Alkane
Cm Alkane
C15 Alkane
C16 Alkane
C17 Alkane
C18 Alkane
C19 Alkane
C20 Alkane
C21 Alkane
C22 Alkane
Alkane
Alkane
Alkane
C2g Alkane '
Biphenyl
3-methyl-biphenyl
Oibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
1-methylphenanthrene
Pyrene
<10*
15
17
12
18
36
14
39
45
42
44
30
23
16
18
36
35
13
19
10
40
<7*
7
<7
9
12
10
10
<7
i*
8
<7
10
<7
<5*
11
+ Che very high waste application occurred on June 19,1983.
* less than the noted detection limit, of the analytical methods when
calculated in terms of these units.
120
-------
TABLE H-4
ORGANIC CONCENTRATIONS IN THE SOILS OF PLOT 14 - A HIGH APPLICATION
PLOT (mg/kg MOISTURE FREE SOIL)+
Organic Compound
Sampling Date
11/9/82
6/6/83
10/25/83
6/6/84
Napthalene
2-methyl-napthalene
1-methyl-napthalene
2,6-dimethyl-napthalene
1,3-dimethyl-napthalene
2,3-dimethyl-napchalene
1,2-diraethyl-napthalene
C8 Alkane
Cg Alkane
CIQ Alkane
Ci! Alkane
Cj2 Alkane
Cj3 Alkane
C14 Alkane
GIS Alkane
C16 Alkane
C}7 Alkane
GIB Alkane
Cjg Alkane
C2Q Alkane
C2i Alkane
C22 Alkane
C23 Alkane
C24 Alkane
C25 Alkane
C2g Alkane "
Biphenyl
3-methyl-biphenyl
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
1-methylphenanthrene
Pyrene
<8*
20
33
43
51
48
40
27
20
11
10
15
8
<8
<10*
<6*
<6*
14
14
10
10
15
+ the high waste application occurred on October 28, 1982.
* less than the noted detection limit of the analytical methods when
calculated in terms of these units.
121
-------
TABLE H-5
ORGANIC CONCENTRATIONS IN THE SOILS OF PLOT 11 - A MEDIUM
APPLICATION PLOT (rag/kg MOISTURE FREE SOIL)+
Sampling Dace
Organic Compound
Napthalene
2-methyl-napthalene
1-methyl-napthalene
2 , 6-dimethyl-napthalene
1 , 3-dimethyl-napthalene
2 , 3-dimethyl-napthalene
1 , 2-dimethyl-napthalene
C8 Alkane
C9 Alkane
C i g Alkane
Cn Alkane
C]^ Alkane
C i 3 Alkane
C1[f Alkane
C i 5 Alkane
C}g Alkane
C}7 Alkane
C18 Alkane
C i 9 Alkane
C2o Alkane
C21 Alkane
C22 Alkane
C23 Alkane
C24 Alkane
C25 Alkane
C2g' Alkane
Biphenyl
3-methyl-biphenyl
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Carbazole
1-methylphenanthrene
Pyrene
11/9/82
<5*
11
11
"
"
11
11
**
**
11
"
"
11
"
14
19
24
28
29
26
18
11
8
9
7
6
<5
"
"
11
"
"
11
"
•i
10/25/83
<5*
fi
11
"
11
"
11
"
11
fi
fi
11
11
"
••
"
'•
"
fi
"
fi
11
fl
*'
"
*"
"
"
"
"
'•
"
11
11
+ the medium application occurred on October 28, 1982.
* less than the noted detection limit of the analytical
methods used when calculated in' terms of these units.
122
-------
TABLE 1-1
AVERAGE EARTHWORM DENSITY FOUND IN THE FIELD PLOTS (number per m2)
Date
1982
June 4**
June 21
July
August
September
October
November
December
1983
March
May
June
July
August
September
October
1984
April
June
July
Natural
Controls
334a*
467a
204a
255a
63a
189a
337a
460a
651a
569a
483a
326a
222a
181a
348a
433a
586a
549a
Type of
Rototilled
Controls
596a
259a
119a
78a
89a
155a
189b
207b
318b
376a
303ab
93b
140b
52b
267b
381a
314b
267b
Application
Low
392a
191a
48a
137a
59a
193a
59b
74C
63C
144b
154b
+
—
—
—
—
—
—
Medium
503a
332a
85a
156a
74a
222a
81b
100C
100C
156b
150b
lb
7C
llc
89C
I19b
65C
123C
High
573a
200a
71a
89a
41a
210a
57b
15C
67^
129b
158b
lb
15C
30C
96C
76"
37C
108C
Very
High
+
—
—
—
—
—
—
—
—
—
—
Ob
4c
4C
4C
14b
14C
Oc
^Densities with a common letcer as a superscript in a horizontal
row are not significantly different for the noted month (P<0.05).
+In June 1983, the low application plots became the very high
application plots.
**Background sample taken before any wastes were applied or the
plots were rototilled.
123
-------
TABLE 1-2
AVERAGE EARTHWORM BIOMASS FOUND IN THE FIELD PLOTS (g/m2)
Type of Application
Dace
1982
May**
June
July
August
September
October
November
December
1983
Mar en
May
June
July
Augus t
September
October
1984
April
June -
July
Natural
Controls
60a*
73a
343
31a
15a
85a
125a
146a
127a
174a
101a
54a
24a
25a
933
119a
122a
U9a
Rototilled
Controls
80a
43a
24ab
14a
13a
61a
50b
46b
74b
L36a
96a
20b
23a
8b
68b
151a
104a
44b
Low
79a
32a
5C
8a
5a
48a
l?c
12C
5C
25b
25b
+
—
—
—
—
—
—
Medium
98a
39a
6C
lla
8a
49a
15C
17^
18C
30 b
25b
2C
lb
lb
llc
41b
29b
37 b
High
90a
31a
17bc
21a
6a
41a
4C
4C
llc
26b
30 b
2C
lb
3b
13C
19b
13b
28b
Very
High
+
—
—
—
—
—
—
—
—
—
—
Oc
6b
2b
Lc
2b
3b
Ob
"Numbers with a common letter as a superscript in a row are not
significantly different for the noted month (P<0.05).
+In June 1983, the low application plots became the very high
application plots.
**Background sample taken before any wastes were applied or the
plots were rototilled.
124
-------
TABLE J-l
METAL CONCENTRATIONS"1" IN EARTHWORMS OF THE NATURAL CONTROL PLOTS
(mg/kg MOISTURE FREE EARTHWORM TISSUE)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ml)
Potassium
(K)
Sodium
(Na)
Titanium
(Tl)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
7,900
±1,100
4
±1
3,500
±800
10
±1
12
±3
9,600
±1,500
12
±2
2,200
±200
180
±39
11
±1
6,900
±740
2,300
ij/0
48
±3
13
±2
220
±51
6/21/82
6,400
±1,800
4
±1
3,500
±650
8
±3
11
±1
7,900
±1,900
9
±2
2,000
±300
110
±30
8
±3
7,500
±1,400
2,800
1 390
36
±17
10
• ±3
260
±66
10/5/82
8,400
±3,200
4
±1
4,200
±750
10
±4
12
±2
10,500
±3,700
13
±4
2,200
±550
240
±120
10
±3
6,100
±900
2,300
±210
23
±6
12
±4
220
±59
11/9/82
6,800
±920
3
±1
3,700
±540
8
±1
12
±2
10,200
±1,000
15
±2
2,100
±150
180
±63
11
±2
7,200
±640
2,700
il50
24
±2
9
±1
240
±47
6/6/83
9,100
±1,400
4
±1
3,700
±600
11
±2
12
-2
9,300
±1,300
9
±2
2,200
±200
170
±40
16
±5
6,400
±2,200
2,600
.=300
68
±15
15
±2
290
±70
10/25/83
10,100
±1,200
4
±1
3,600
±200
13
±2
10
±1
11,400
±1,300
9
±1
2,400
±200
210
±40
12
±2
5,700
±300
2,400
r400
37
±13
16
±2
270
±50
6/6/84
8,100
±1,300
3
±0
3,700
±600
10
±2
11
±1
9,700
±1,100
7
±L
2,000
±200
180
±42
9
±1
6,000
±500
2,300
i200
45
±15
13
±2
260
±38
+ Average and standard deviation of the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
125
-------
TABLE J-2
METAL CONCENTRATIONS* IN EARTHWORMS OF THE ROTOTILLED CONTROL PLOTS
(mg/kg MOISTURE FREE EARTHWORM TISSUE)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Mi)
Potassium
(K)
Sodium
(Ma)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
6,300
±650
5
±2
3,300
±180
7
±1
12
±1
7,800
±71
11
±2
2,000
±43
150
±45
10
±3
7,300
±1,300
2,700
±320
39
ill
10
±1
310
±70
6/21/82
3,700
±320
5
±1
2,600
±810
15
±18
29
= 3
5,900
± 1 , 000
30
±4
1,900
±680
110
±20
6
±1
7,100
±1,200
3,200
r4iO
45
i!3
8
±3
280
±47
10/5/82
11,600
±2,900
3
±1
3,500
±500
13
±2
13
±3
13,700
±1,500
15
±2
2,700
±240
240
±81
13
±1
5,500
±1,200
1,900
i370
34
±5
16
±3
180
±12
11/9/82
6,300
±1,900
5
±0
6,000
±2,990
9
±1
11
±0
8,400
±2,000
15
±7
2,100
±270
190
±76
10
±1
6,200
±1,500
2,600
£690
27
±4
10
±1
350
±20
6/6/83
12,100
±1,400
4
±1
3,600
±410
16
±3
12
±2
12,200
±700
11
±2
2,600
±200
240
±66
17
±5
7,000
±240
2,500
±260
84
±13
19
±3
250
±33
10/25/83
10,000
±1,600
4
±1
3,800
±700
12
±2
11
±3
11,500
±2,000
9
±1
2,400
±300
213
±28
27
±7
5,500
±1,400
2,700
±700
44
±15
16
±3
220
±42
6/6/84
8,400
±1,100
3
±0
3,900
±400
12
±3
10
tl
10,300
±1,400
8
±1
2,100
±200
210
±63
10
±2
6,000
±700
2,300
£400
37
±8
13
±2
230
±22
+ Average and standard deviation of the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
126
-------
TABLE J-3
METAL CONCENTRATIONS* IN EARTHWORMS OF THE LOW APPLICATION PLOTS
(mg/kg MOISTURE FREE EARTHWORM TISSUE)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
5,000
±880
3
±1
4,400
±1,600
6
±1
11
±3
6,200
±620
10
±5
1,800
±180
150
±24
9
±4
8,400
±870
2,900
il90
40
H5
8
±1
260
±32
6/21/82
5,400
±2,500
6
±2
2,600
±410
14
±8
20
±11
6,500
±3,300
23
±20
1,700
±280
110
±50
14
±8
7,300
± 1 , 900
2,700
:170
102
±10
16
±7
320
±90
10/5/82
8,700
±1,600
3
±2
5,100
±2,400
11
±3
13
±2
11,100
±2,400
16
±2
2,300
±330
210
±55
11
±2
6,300
±980
2,400
2:470
22
±1
12
±2
250
±38
11/9/82
5,900
±1,220
7
±2
4,000
±860
8
±0
17
±6
8,000
±1,400
15
±0
1,900
±190
150
±24
12
±1
8,000
±600
3,900
2290
_**
8
±0
230
±70
6/6/83
9,400
±2,100
9
±5
3,600
±600
24
±11
26
±12
8,800
±1,400
25
±13
2,200
±200
170
±46
18
±6
6,500
±2,200
3,100
i600
140
±60
18
±4
300
±49
+ Average and standard deviation of the data from the four plots
on the noted sampling data.
* Background sample taken before any wastes were applied or the
plots were rototilled.
**Less than the noted detection limit of the analytical methods
when calculated in terms of these units.
127
-------
TABLE J-4
METAL CONCENTRATIONS* IN THE EARTHWORMS OF THE MEDIUM APPLICATION PLOTS
(mg/kg MOISTURE FREE EARTHWORM TISSUE)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Mi)
Potassium
(K) "
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
5,900
±770
4
±2
3,700
±960
7
±1
10
±1
7,400
±1,200
8
±1
1,800
±190
140
±32
8
±2
7,300
±580
2,600
.070
32
±10
9
±1
230
±32
6/21/82
5,900
±2,300
5
±1
3,200
±300
11
±4
16
±4
7,400
±2,300
19
rll
1,900
±290
140
±52
11
±4
8,200
±1,100
3,500
j:360
79
±51
12
±3
240
±25
10/5/82
8,900
±1,800
4
±1
4,700
±1,800
13
±2
36
±4
10,800
±1,800
16
±6
2,300
±130
210
±51
12
±3
6,400
±1,600
2,700
;6<*0
29
±9
12
±3
240
±58
11/9/82
7,600
±3,400
4
±1
3,100
±560
11
±2
12
±1
8,700
±4,100
12
±0
1,900
±450
180
±38
12
±2
6,900
±2,200
3,200
.= 1,600
28
±0
12
±3
430
±320
6/6/83
9,200
±1 , 800
6
±3
3,800
±500
18
±14
17
±6
9,100
±1,500
19
±9
2,200
±100
150
±46
18
±5
6,500
±600
2,800
i300
100
±41
16
±1
230
±21
10/25/83
11,000
±3,000
5
±2
4,400
±700
20
±0
12
±0
11,600
±3,100
**
2,600
±500
178
±70
17
±0
6,500
±800
2,900
.=400
80
±0
23
±0
220
±8
6/6/84
9,500
±1,100
3
±1
5,100
±700
19
±5
12
±1
10,700
±1,200
10
±1
2,200
±100
205
±60
10
±2
6,100
±500
2,400
j:200
57
±15
14
±3
390
±120
+ Average and standard deviation of the data from the four plots on the
noted sampling data.
* Background sample taken before any wastes were applied or the plots
were rototilled.
** Less than the noted detection limit of the analytical methods when
calculated in terms of these units.
128
-------
TABLE J-5
METAL CONCENTRATIONS'1" IN THE EARTHWORMS OF THE HIGH APPLICATION PtOTS
(mg/kg MOISTURE FREE EARTHWORM TISSUE)
Sampling Date
Metal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K) "
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
6/4/82*
6,800
±1,500
4
±1
4,300
±1,400
8
±2
12
tl
5,900
±2,700
8
±2
2,100
±270
240
±100
9
±2
7,300
±860
2,600
±230
39
no
11
±3
230
±30
6/21/82
3,500
±1,400
5
±3
2,900
±440
7
±4
12
±2
7,800
±3,100
11
±3
1,800
±470
160
±70
8
±3
7,100
±520
3,200
z270
34
±20
9
±5
250
±30
10/5/82
11,400
±1,500
3
±1
4,300
±1,500
19
±7
16
±4
13,800 ±
±500
21
±15
2,600
±96
300
±64
16
±6
5,700
±1,100
2,600
£350
40
±6
16
±2
220
±45
11/9/82
8,300
±0
6/6/83
1,300
±2,500
_** 4
-
7,000
±0
-
-
-
-
14,000
±0
-
-
2,700
±0
300
±0
-
-
6,200
±0
2,700
iO
-
-
—
-
240
±0
±1
3,400
±500
21
±8
12
±1
±12,500
±1,500
15
±6
2,600
±300
250
±72
20
±9
6,800
±600
2,900
±200
120
±28
20
±6
200
±60
10/25/83
9,000
±4,100
6
±3
4,500
±900
19
±3
15
±3
10,100
±4,400
15
±0
2,200
±600
280
±150
16
±1
6,400
±700
3,200
±600
80
±8
19
±2
200
±65
6/6/84
8,700
±1,500
4
±1
5,100
±900
21
±7
14
±2
9,700
±1,700
10
±2
2,100
±200
210
±27
11
±3
5,900
±600
2,500
1200
57
±15
14
±3
390
±100
+ Average and standard deviation of the data from the four plots on the
noted sampling data.
* Background sample taken before any wastes were applied or the plots
were rototilled.
** Less than the noted detection limit of the analytical methods when
calculated in terms of these units.
129
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TABLE J-6
METAL CONCENTRATIONS* IN EARTHWORMS FROM THE VERY HIGH APPLICATION PLOTS
(rag/kg MOISTURE FREE EARTHWORM TISSUE)
Mecal
Aluminum
(Al)
Cadmium
(Cd)
Calcium
(Ca)
Chromium
(Cr)
Copper
(Cu)
Iron
(Fe)
Lead
(Pb)
Magnesium
(Mg)
Manganese
(Mn)
Nickel
(Ni)
Potassium
(K)
Sodium
(Na)
Titanium
(Ti)
Vanadium
(V)
Zinc
(Zn)
Sampling
6/6/83
9,400
±2,100
4
±1
3,600
±400
16
±3
12
±2
12,200
±700
11
±2
2,600
±200
240
±66
17
±5
7,000
±200
2,500
1 300
84
±13
19
±3
250
±33
Date
6/6/84
3,500
±1,200
4
±0
6,300
±1,300
12
±3
10
±1
10,300
±1,400
8
±1
2,100
±200
210
±63
10
±2
6,000
±700
2,300
±400
37
±8
13
±2
232
±22
+ Average and standard deviation of the data from the four plots on the
noted sampling data.
130
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TABLE K-l
QUALITY ASSURANCE ANALYSES OF THE STANDARD SLUDGE SUPPLIED BY THE
PROJECT OFFICER - OIL AND GREASE RESULTS
Dace of
Analysis
1983
1/9
2/9
2/10
2/14
3/25
6/14
7/3
8/1
8/15
8/19
11/2
12/2
Average
Oil and Grease*
(g/kg MFS)
44.98
44.10
44.42
44.10
43.50
49.16
47.62
51.22
52.60
52.88
49.28
45.00
Ave rage
Date of Oil and Grease*
Analysis (g/kg MFS)
1984
1/26 45.98
3/1 50.07
6/3 48.14
6/7 51.14
7/2 48.55
*Two samples of Che scandard sludge were analyzed on each dace.
Note: 95% of these data were within one standard deviation of the
mean and all of the data were within two standard deviations
of the mean.
The average oil and grease concentration and 95% confidence
limits for the standard sludge, as supplied by EPA, were:
average = 52.68 g/kg MFS, 95% limits = 26.1 to 79.3 g/kg MFS.
The results obtained from these quality assurance evaluations
were: average = 47.7 g/kg MFS, 95% limits = 46.3 to 49.2 g/kg MFS.
131
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