estoring Hazardous Spill-Damaged Areas
echnique Identification/Assessment
tlantic Research Corp.
lexandria, VA
repared for
unicipal Environmental Research Lab.
"¦incinnati, OH
Jep 81
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
NTS
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EPA-600/2-81-208
September 1981
P B 82-103 870
RESTORING HAZARDOUS SPILL-DAMAGED AREAS
Technique Identification/Assessment
by
Randall S. Wentsel
Roberta H. Foutch
William E. Harward, III
William E. Jones, III
Judith F Kitchens
Atlantic Research Corporation
Alexandria, Virginia 22314
Contract No. 68-03-2648
Project Officer
Jolm 3ru£ger
Oil and Hazardous Materials Spills Branch
Municipal Environmental Research Laboratory - Cincinnati
Edison, New Jersey 08837
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
REPRODUCED B*
NATIONAL TECHNICAL
INFORMATION SERVICE
US DEPAR1MEN1 OF COMMERCE
SpRINGflElD V« 22161
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NOTICE
THIS DOCUMENT HAS BEEN REPRODUCED
FROM THE BEST COPY FURNISHED US BY
THE SPONSORING AGENCY. ALTHOUGH IT
IS RECOGNIZED THAT CERTAIN PORTIONS
ARE ILLEGIBLE, IT IS BEING RELEASED
IN THE INTEREST OF MAKING AVAILABLE
AS MUCH INFORMATION AS POSSIBLE.
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TECHNICAL REPORT DATA
(Please read Intiructiom on the reverie before completing)
1 REPORT no
EPA-600/2-81- 208
ORD Rertnrt
4 TITLE ANO SUBTITLE
Restoring Hazardous Spill-Damaged Areas
Technique Identification/Assessment
3 ocriPi££jT S ACCESSIOf*NO
_ PB8Z ! 0 ?87 0
3 hEPORT OATE
Septemoer 1981
8. PERFORMING ORGANIZATION COOE
V.USTr°Wentsel, R.H. Foutch, W.E. Harward, III, W.E.
Jones, III and J.F. Kitchens
8 PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME ANO AOORESS
Atlantic Research Corporation
5390 Cherokee Avenue
Alexandria, Virginia 22314
10 PROGRAM ELEMENT NO
AZB1B
11 CONTRACT/GflANT NO
Contract No. 68-03-2648
12 SPONSORING AGENCY NAME ANO AOORESS
Municipal Environmental Research Laboratory- Cln.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
OH
13. TYPE OF REPORT ANO PERtOO COVERED
Final
14 SPONSORING AGENCY COOE
EPA/600/14
15 supplementary notes
Project Officer: John E.
Brugger (201)321-6634
COLOR ILLUSTRATIONS ARE
REPRODUCED IN BLACK & WHITE
is abstract goal of this study was to identify and assess methods that could be
used to accelerate the restoration of lands damaged by spills of hazardous materials.
The literature was reviewed to determine what response methods had been used in the
past to clean up spills on land and identify other techniques that could be developec
for detoxification of hazardous, spill-damaged lands.
Four biological techniques were evaluated for accelerating the restoration of
spill-damaged lands in the laboratory for Phase II. The techniques and the chemicals
used were the following:
I. Enhancement of microbial degradation by indigenous
organisms
II. Addition of mixed microorganisms from primary sewage
III. Addition of adapted/mutant microbial cultures
IV. Selective absorption by harvestable plants
The accelerated removal of one or both chemicals was observed in techniques II, III,
and IV. The effects of the spilled chemical on the soil chemistry and microorganisms
were also monitored.
In Phase III, a plan for field testing of techniques II and IV was designed.
Recoiranended land restoration methods for spills of the 271 hazardous chemicals listec
in the Federal Register (1978) were also compiled in Phase IV.
chlorobenzene, Ethion
formaldehyde, aniline
dinitrophenol .chlordanje
lead, cadmium
<£Y WOROS ANO OOCUMENT ANALYSIS
DESCRIPTORS
b IOENT1FIERS/OPEN ENOEO TERMS
c COSAT1 Field/Croup
biodegradation
hazardous chemicals
land restoration
chemical spills
land restoration
hazardous spills:
chlorobenzene
dinitrophenol, ethion,
chlordane, formaldehyde
cadmium, lead, aniline
13B
13 DISTRIBUTION STATEMENT
Distribution Unlimited
19 SECURITY CLASS (This Report)
UNCLASSIFIED
20 SECURITY CLASS (Thu pa?e)
UNCLASSIFIED
EPA Form 2220-1 (9-73)
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
li
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FOREWORD
The U S. Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health and
welfare of the American people Noxious air, foul water, and spoiled land are
tragic testimonies to the deterioration of our natural environment. The
complexity of that environment and the interplay of its components require a
concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solution;
it involves defining the problem, measuring its impact, and searching for
solutions. The Municipal Environmental Research Laboratory develops new and
improved technology and systems to prevent, treat, and manage wastewater and
solid hazardous waste pollutant discharges from municipal and community sources,
to preserve and treat public drinking water supplies, and to minimize the adverse
economic, social, health, and aesthetic effects of pollution. This publication
is one of the products of that research and provides a most vital communications
link between the researcher and the user community.
This report presents the results of an investigation of four techniques
for accelerating the natural recovery of hazardous chemical spill-damaged land.
Three of the techniques involve the use of microorganisms to decompose the haz-
ardous chemical; a fourth technique utilizes plants to bioaccumulate heavy
metal compounds. The report will be of interest to all those involved with
spill cleanup and soil biology.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
iii
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ABSTRACT
This study identifies and assesses methods for accelerating the restora-
tion of lands damaged by spills of hazardous materials. The first phase of the
study involved a literature review to determine what response methods had been
used in the past to clean up spills on land and to identify other techniques
that could be developed for detoxification of hazardous spill damaged lands.
Four primarily biological techniques for accelerating the restoration of
spill-damged lands were evaluated in the laboratory during the second phase
of the study. The techniques and the chemicals used were the following:
Technique Chemical
I. Enhancement of microbial degradation chlorobenzene
by indigenous organisms Ethion
II. Addition of mixed microorganisms from formaldehyde
primary sewage effluent aniline
III. Addition of adapted/mutant microbial dinitrophenol
cultures chlordane
IV. Selective absorption by harvestable lead nitrate
plants cadmium nitrate
The accelerated removal of one or both chemicals was observed in tech-
niques II, III, and IV. The effects of the spilled chemical on the soil chem-
istry and microorganisms were also monitored.
During the third phase, a plan for field testing of techniques II and IV
was designed. Recommended land restoration methods for spills of the 271 haz-
ardous chemicals listed in the Federal Register (1978) were compiled during
the fourth phase.
This report was submitted in partial fulfillment of Contract No. 68-03-
2648 by Atlantic Research Corporation under subcontract to Rockwell Interna-
tional Corporation, Environmental Monitoring & Services Center, Newbury Park,
California, under the sponsorship of the U.S. Environmental Protection Agency.
This report covers the period 7 February 1979 to 1 August 1980, and work was
completed as of 15 December 1980.
iv
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CONTENTS
Foreword iii
Abstract iv
Figures vii
Tables xi
Abbreviations and Symbols xv
Acknowledgment xvii
1. Introduction 1
2. Conclusions 3
3. Recommendations 6
4. Literature Review of Hazardous Spills on Land
and Restoration Methods Employed 7
Identification of Hazardous Spills on Land 7
PCB Spill, Kingston, Tennessee 13
Acrylonitrile Spill, Leon, Kentucky 23
Phenol Spill, Slabtown, Maryland 37
Acrylonitrile Spill, Dayton, Ohio 47
Nitric Acid Spill, Estill, South Carolina 52
Caustic Soda Spill, Duffee, Mississippe 55
Formalin Spill, Rensselaer County, New York 57
Toluene Spill, Wallsburg, Utah 70
Arsenic Trioxide Spill, Elkhorn, Wisconsin 70
Conclusions on Land Restoration Methods 79
5. Fate of Hazardous Material Spills on Land and
Potential Restoration Methods 81
Fate of Hazardous Materials Spilled in the Environment. . 81
Restoration of Spill-Damaged Lands: Previously ... 81
Used Techniques 81
6. Selection of Chemicals for Evaluation of
Land Restoration Techniques 116
7. Experimental Methodology 118
Environmental Chamber Construction 118
Chemical Spills in Environmental Chambers 121
Land Restoration Techniques 124
Sampling Methodology 127
Analytical Procedures 127
8. Experimental Results 135
Introduction 135
Land Restoration Technique I - Monochlorobenzene Spill. . 135
Land Restoration Technique I - Ethion Spill 144
Land Restoration Technique II - Formaldehyde Spill . . . 159
Land Restoration Technique II - Aniline Spill 170
v
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CONTENTS (continued)
Land Restoration Technique III - Chlordane Spill 179
Land Restoration Technique III - 2,4-Dinitrophenol Spill . 184
Land Restoration Technique IV - Cadmium Nitrate
and Lead Nitrate Spill 188
9. Evaluation of the Land Restoration Techniques 194
10. Field Demonstration Test Design 196
Site Selection and Pretest Preparation - Task I 196
Land Restoration After a Formaldehyde Spill - Task II. . . 197
Land Restoration After an Aniline Spill - Task III .... 202
Land Restoration After a Spill of Cadmium
Nitrate - Task IV 203
11. Operating Procedures for Restoration of Spill-Damaged Lands . . 204
Assessing the Damage to the Land 223
Selection of the Appropriate Land Restoration Technique. . 223
Application of the Land Restoration Technique 223
References 229
Appendices
A. Background Data on Hazardous Chemicals Used in Laboratory Tests . 235
B. Monochlorobenzene Data 252
C. Ethion Data 269
D. Formaldehyde Data 298
E. Aniline Data 321
F. Chlordane Data 343
G. 2,4-Dinitrophenol Data 348
H. Cadmium Nitrate and Lead Nitrate Data 353
vi
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FIGURES
Number Page
1 Topography of Spill Site, Kingston, Tennessee 15
2 Temperature of Three Soil Types with Depth, Kingston,
Tennessee 19
3 Solvent Concentration Profile - Well Located Closest to PCB
Spill Site 22
4 Acrylonitrile Spill Near Leon, Kentucky - Topography of Area .... 29
5 Spill Site Shortly After Derailment 30
6 Numbered Soil Sampling Locations in Spill Area (a and b) 33
7 Topography of Phenol Spill Area, Slabtown, Maryland 39
8 Detailed Map of Phenol Spill Site and Sampling Location 40
9 Topography of Acrylonitrile Spill Area, Dayton, Ohio 49
10 Detailed Map of Spill Site 51
11 Topography of Nitric Acid Spill Site, Estill, South Carolina .... 54
12 Topography of Caustic Soda Spill Site, Duffee, Mississippi 59
13 Topography of Formaldehyde Spill Site, Rensselaer County,
New York 63
14 Spill Area and Sampling Stations 67
15 Topography of Toluene Spill Area, Wallsburg, Utah 72
16 Topography of Arsenic Trioxide Spill Site, Elkhorn, Wisconsin. ... 75
17 Disappearance of Malaoxon m Sterile and Non-Sterile Soil
Samples at pH 6.2, 7.2 and 8.2 90
18 Disappearance of Malathion in Sterile and Non-Sterile Soil
Samples at pH 7.2 91
vii
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FIGURES (continued)
19 Effect of the Level of Crude Oil Addition to the Soil in the
Germination of Maize Grains 104
20 Diagram of Trace-Metal Cycling in a Plant-Environmental
System 105
21 Dose-Response Curves of Seedling Lettuce Subjected to Acute
Zinc and Copper Toxicity 106
22 Set of Three Environmental Chambers 119
23 Environmental Chambers 120
24 Water-Cooled Condenser, Carbon Filter and Sodium Hydroxide
Bubbler from Spill Chamber 120
25 Experimental Design for Plant Uptake Studies 122
26 Upper-Level Organic Soil Microbial Populations - Monochloro-
benzene Spill 137
27 Upper-Level Sandy Soil Microbial Population - Monochlorobenzene
Spill 138
28 Upper-Level Clay Soil Microbial Population - Monochlorobenzene
Spill 139
29 Monochlorobenzene Concentrations in the Organic Soils 141
30 Monochlorobenzene Concentrations in the Sandy Soils 142
31 Monochlorobenzene Concentrations in the Clay Soils 143
32 Upper-Level Organic Soil Microbial Populations - Ethion Spill . . . 146
33 Upper-Level Sandy Soil Microbial Populations - Ethion Spill .... 150
34 Upper-Level Clay Soil Microbial Populations - Ethion Spill 152
35 Upper-Level Ethion Concentrations in Organic Soil 154
vin
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FIGURES (continued)
36 Upper-Level Ethion Concentrations in Sandy Soil 155
37 Upper-Level Ethion Concentrations in Clay Soil 156
38 Upper-Level Organic Soil Microbial Populations - Formaldehyde
Spill 160
39 Upper Level Sandy Soil Microbial Populations - Formaldehyde
Spill 161
40 Upper-Level Clay Soil Microbial Populations - Formaldehyde
Spill 162
41 Formaldehyde Concentrations in Upper Layer of Organic Soils .... 166
42 Formaldehyde Concentrations in Upper Layer of Sandy Soils 167
43 Formaldehyde Concentrations in Upper Layer of Clay Soils 168
44 Upper-Level Organic Soil Bacterial Populations - Aniline Spill. . . 172
45 Upper-Level Sandy Soil Bacterial Populations - Aniline Spill. . . . 173
46 Upper-Level Clay Soil Bacterial Populations - Aniline Spill .... 174
47 Aniline Concentrations - Upper Level of Organic Soil 175
48 Aniline Concentrations - Upper Level of Sandy Soil 176
49 Aniline Concentrations - Upper Level of Clay Soil 177
50 Chlordane Concentrations in Upper Level of Organic Soil 180
51 Chlordane Concentrations in Upper Level of Sandy Soil 181
52 Chlordane Concentrations in Upper Level of Clay Soil 182
53 2,4-Dinitrophenol Concentrations in the Upper Level of the Organic
Soils 185
ix
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FIGURES (continued)
54 Dinitrophenol Concentrations in the Upper Level
of the Sandy Soils 186
55 Dinitrophenol Concentrations in the Upper Level
of the Clay Soils 187
56 Test Plot Design 198
57 Logic Tree for Selection of Appropriate Restoration Techniques . . . 224
x
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TABLES
Number Page
1 Land Spills of the 271 Hazardous Chemicals 1975-1977 8
2 Background of PCB Spill, Kingston, Tennessee 14
3 Weather Conditions-Kingston, Tennesse, Area 16
4 Monthly Precipitation Levels from 1973-1975 at PCB Spill Area .... 17
5 Comparison of Analytical Data from Core Samples Collected in
in 1973 and 1975 20
6 Microbial Populations Relative to pH of Soil Samples 24
7 Microbial Populations Relative to Moisture Content of Soils 25
8 Microbial Populations Relative to Soil Types 26
9 Microbial Populations Relative to PCB Concentration in Core
Samples 27
10 Background of Acrylonitrile Spill, Near Leon, Kentucky 28
11 Weather Conditions, Leon, Kentucky 32
12 Acrylonitrile Levels in Surface Soil Samples 35
13 Acrylonitrile Levels in Soil Cores 36
14 Background of Phenol Spill, Slabtovn, Maryland 38
15 Weather Conditions of Slabtown, Maryland 41
16 Weather Conditions After the Spill in Slabtown, Maryland 42
17 Phenol Levels Through Treatment System and Jennings Run 44
18 Phenol Levels in Soil Samples 46
19 Background of Acrylonitrile Spill, Dayton, Ohio 48
xi
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20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
50
53
56
58
60
61
62
65
66
68
69
71
73
74
76
78
80
84
86
88
TABLES (continued)
Weather Conditions, Dayton, Ohio
Background of Caustic Soda Spill, Estill, South Carolina . .
Weather Conditions, Estill, South Carolina
Background of Caustic Soda Spill, Duffee, Mississippi . . .
Weather Conditions, Duffee, Mississippi
Soil pH levels After Treatment with Alum
Background of Formalin Spill, Rensselaer County, New York
Weather Conditions - Rensselaer, New York
Weather Conditions After Spill
Formaldehyde Levels in the Soil Samples
Formaldehyde Levels in Marsh Soil and Water Samples
Background on Toluene Spill, Wallsburgh, Utah
Weather Conditions, Wallsburh, Utah
Background of Arsenic Trioxide Spill, Elkhorn, Wisconsin . .
Weather Conditions, Elkhorn, Wisconsin
Weather Conditions After the Spill
Treatment Methods for Hazardous Material Spills
Microorganisms Reported to Degrade Pesticides
Types of Pesticide Transformation in Soil and/or Plants. . .
Percentage of Chemical and Microbial Degradation of Malathion
in Soil After 10 Days
xii
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TABLES (continued)
40 Insecticide Absorption by Sweet Potatoes and Uhite Potatoes
from Treated Soil 94
41 Persistence of Pesticides in Soil 97
42 Biodegradation of ^C-carboxyl EDTA in a Variety of Soils 98
43 Effect of Various Fungicide Treatments on Seed Germination
Seedling Injury and Chromosome Abberations in Barley 100
44 The Types and Frequency of Chromosomal Abberations Produced
by a 30 min. Treatment with Various Fungicides in the
Secondary Roots of Vicia Faba 102
45 Typical Distribution Among Plant Parts of Phaseolus Vulgaris
L. of Some Trace Metals 1-07
46 Forage Yields and Uptake of Phosphorus and Heavy Metals by Corn
as Affected by Soil pH and Inclusion of Heavy Metals in
Reagent-Grade Diammonium Phosphate 109
47 Total Yield and Concentrations of Heavy Metals in Vegetables,
as Affected by Sludge Treatment 110
48 Upper-Layer Fungal Counts - Ethion Spill 147
49 Ethion Related Residues 158
50 Upper-Layer Fungal Counts - Formaldehyde Spill 1^3
51 Rate of Formaldehyde Loss 1^0
52 Loss Rate of C-14 Activity 17®
53 Half-Lives of Aniline in Organic and Sandy Soils 1?8
14
54 14 Radiation Counts in Sandy Soils Treated with C
Chlordane 1®^
55 Average Soil Concentrations of Cadmium and Lead 189
xiii
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TABLES (continued)
56 Lead Levels in Plants as a Function of Soil Type and Treatment. . . 190
57 Cadmium Levels in Plants as a Function of
Soil Type and Treatment 191
58 ANOVA: Latin Square Design 200
59 ANOVA: Factorial Experiment with Blocking 201
60 ANOVA: Two-Way Analysis 201
61 Hazardous Chemical Classification and Applicable
Restoration Techniques 205
62 Vegetation Recommendations to Cover Land Contaminated
With Hazardous Materials 228
xiv
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ABBREVIATIONS AND SYMBOLS
A
-
acre
AgN03
-
silver nitrate
ANOVA
-
analysis of variance
BOD5
-
5-day biological oxygen demand
14C
-
radio labelled carbon
CA (N03)2
-
calcium nitrate
cc/min
-
cubic centimeters per minute
Cd(N03)2
-
cadmium nitrate
CEC
-
cation exchange capacity
cm
-
centimeter
CO 2
-
carbon dioxide
cpm
-
counts per minute
COD
-
chemical oxygen demand
2,4,-D
-
(2,4-Dichlorophenoxy) acetic acid
2,4,5-T
-
(2,4,5-Trichlorophenoxy) acetic acid
DBCP
-
1,2-Dibromo-3-Chloropropane
DDE
-
dichlorodiphenyldichloroethylene
DDT
-
l,l,l-Trichloro-2, 2-bis (£-chlorophenyl) ethane
DNBP
-
4,6-Dinitro-o-sec-butylphenol
DSMA
-
disodium monomethlarsonate
EDTA
-
ethylenediaminetetraacetic acid
FeCl3
-
ferric chloride
GC
-
gas chromatography
g 2
-
gram
g/cm
-
gram per square centimeter
G.E.
-
General Electric
ha
-
hectare
H3BO3
-
boric acid
ID
-
inner diameter
IR
-
infrared
kg
-
kilogram
kh2po4
-
mono potassium phosphate
k2hpoa
-
dipotassium phosphate
KOH
-
potassium hydroxide
LB
-
pound
LC50
-
concentration which kills 50% of treated population
LD50
-
dose which kills 50% of treated population
LDL0
-
largest dose nonlethal to treated population
m
-
meter
M
-
molar
mm Hg
-
millimeters of mercury
u
-
micro
xv
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ABBREVIATIONS AND SYMBOLS (continued)
pm
-
micrometer
min
-
minute
ml
-
milliliter
mg/kg
-
milligrams per kilogram
MgCl2
-
magnesium chloride
mCi
-
millicurie
yCi
-
microcurie
M.A.C.
-
maximum allowable concentration
n2
-
nitrogen
nm
-
nanometer
NMR
-
nuclear magnetic resonance
NH4HO3
-
ammonium nitrate
NaOH
-
sodium hydroxide
n.s.i.
-
no specific isomer
OSC
-
on-scene coordinator
Pa
-
Pascals, unit of pressure
PCB
-
polychlorinated biphenyl
PCP
-
pentachlorophenol
PH
-
measure of acidity or basicity
PMA
-
acetoxyphenylmercury
PPb
-
parts per billion
ppm
-
parts per million
RTV
-
room temperature vulcanizing silicone rubber
sp.
-
species
torr
-
unit of pressure = mm Hg (0 C)
TLV
-
threshold limit value
TLm
-
median tolerance limit
txs
-
treatment-sampling time interaction
<»>
-
less than, more than
ABBREVIATIONS
FOR TABLE 61
s - water soluble to the extent of greater than 50 ppm
i - water insoluble less than 50 ppm
b - biodegradable with incomplete mineralization and a half-life
in soil (actual or predicted) of less than A months
r - chemically or photochemically reactive
t - biotransformed organic
u - biouseable inorganic
v - volatile from soil due to high vapor pressure, codistillation
with water, water insolubility
p - persistent toxic residue
n - persistent non-toxic residue
xv i
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ACKNOWLEDGMENT
This work was performed under subcontract to the Environmental Monitor-
ing & Services Center of Rockwell International, Newbury Park, California.
The authors wish to thank George R. Schneider, Project Manager, Environmental
Monitoring & Services Center, and John E. Brugger, Project Officer, U.S. En-
vironmental Protection Agency, for their direction and support.
xvii
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SECTION 1
INTRODUCTION
The spill of a hazardous chemical on land can produce long-term damage to
the area affected. The plants and organisms exposed to concentrated doses of a
chemical will usually be eradicated from the spill area for some time. Natural
recovery of spill damaged land is a slow process that can take years. In
addition, if erosion or leaching of nutrients from the area occurs, the land can
become permanently scarred. If the chemical leaches into the groundwater, an
entire watershed can become contaminated.
The rapid restoration of chemically damaged land will reduce the danger of
further contamination and prevent the land from being permanently affected.
The present study focused on the identification and development of
biological techniques which have the potential for restoration of spill damaged
lands and a laboratory assessment of the feasibility of these techniques. A
literature search was conducted to determine the current biological, chemical
and physical techniques used to treat spill damaged land. Viable biological
techniques were then identified and four were selected for laboratory evalua-
tion
The first technique studied was the enhancement of microbial degradation by
indigenous organisms. This technique was tested for several reasons. First, the
microorganisms which have survived the initial shock from the spilled chemical
are relatively resistant to the chemical. If the surviving microbial population
can be increased rapidly with the addition of nutrients, then they may be able to
degrade the chemical. Also, the organisms used are from the spill area and do not
have to be specially cultured
The second technique evaluated the use of microorganisms in primary sewage
effluent to degrade a spilled chemical. Primary sewage effluent has a variety of
microorganisms present in it and the effluent is usually high in nutrients.
Primary sewage effluent can be used to replenish the microbial population in the
spill area. If nutrients are added, the microorganisms from the primary sewage
effluent can degrade the chemical. In addition, primary sewage effluent is cheap
and readily available.
The third technique was the addition of adapted/mutant microbial cultures.
For this method soil or primary sewage effluent microorganisms were cultured in
nutrient medium containing the chemical to be degraded. The chemical was the
sole carbon source for the organisms. After several subcultures, a culture was
developed that could utilize the chemical of concern. This culture, with
nutrients, can then be applied to the soil to degrade the spilled chemical.
1
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The final technique evaluated was the uptake of heavy metals by harvestable
plants. Plants were selected for use based on data from the literature search and
preliminary tests. For the heavy metal contaminated soil, conditions for uptake
by the plants were optimized by adjusting the pH and by adding a chelating agent.
A plan for field testing of the two most promising techniques from the
laboratory tests was then developed. The plan included the chemicals to be
spilled, restoration treatments to be applied, and sampling techniques.
Finally, recommended land restoration methods were developed for the
hazardous chemicals under consideration. The chemicals were environmentally
classified and restoration techniques were proposed for treatment.
2
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SECTION 2
CONCLUSIONS
Four biological techniques were investigated for the restoration of spill-
damaged lands. Three of these techniques were concerned with the use of
microorganisms to degrade hazardous chemicals adsorbed in soil. The fourth
technique involved terrestrial plants as a means of removing heavy metal
contamination from soils by bioaccumulation. The investigations were conducted
with three different types of soil, organic, sandy and clay.
The technique of using microbial populations, present in the soil at the
spill site, to degrade volatile, non-water soluble, low polarity compounds, such
as monochlorobenzene, was found to be ineffective. Before bacterial populations
could adapt to and degrade the somewhat volatile chemical, it had evaporated from
the soil.
Ethion, an organo-phosphorus pesticide, was the second chemical which
tested the use of indigenous microbial populations to degrade a chemical. After
the Ethion spill the microbial populations decreased. The decrease was most
likely due to the suffocation of the organisms or the lower pH of the soil after
the spill. The application of nutrient broth and soil pH adjustments to near
neutral levels were successful in increasing the indigenous microbial popu-
lations in the treated chambers. However, the microorganisms surviving the
Ethion spill were unable to attack and degrade the Ethion.
Treatments to increase the availability of Ethion to the microbial
population were then conducted. The applications of Tween 80 and ethanol to the
soils were expected to increase the water solubility of the Ethion. It was
anticipated that the increased solubility would lead to a higher biodegradation
rate However, the Ethion concentration in the soil did not drop substantially
after the treatment.
Soil pH values were then adjusted to basic levels, initially between 9 and
10 units. When this treatment proved ineffective for increasing the rate of
hydrolysis of Ethion, a severe treatment using approximately 50% ethanol and 8%
NaOH solution was used to chemically breakdown the Ethion. This treatment
substantially reduced the Ethion levels in the organic and sandy soils, but not
in clay soil. However, a treatment this severe could only be used in small spill
areas under carefully controlled conditions Once the concentration of the
hazardous chemical has been reduced to tolerable levels, the soil would have to
be neutralized, reseeded with a mixed population of microorganisms and revege-
tated.
3
-------
Although the technique of adding spill resistant strains of indigenous
microbes with the expectation that these microbes will degrade the spilled
chemical, was unsuccessful for monochlorobenzene and Ethion. The ability of soil
microorganisms to degrade many of the simpler chemicals such as ammonium acetate
has long been established
In Technique II, mixed cultures of microorganisms from primary sewage
effluent were evaluated for their ability to hasten the degradation of
formaldehyde and aniline in various soil types.
The accelerated removal of formaldehyde from the soil by treatment of the
spill damaged area with primary sewage effluent and a mixed microbial cultures
containing primarily Pseudomonas sp. was moderately successful. Both treatments
increased the rate of formaldehyde removal from sandy and clay soils after the
second application. It appears from the data, that the treatments are useful at
formaldehyde levels less than 2000 ppm. In organic soils, sufficient nutrients
were available to promote residual microbial growth without reinoculating the
soil. However, this recovery only happens when formaldehyde levels fall below
1000 ppm. Microbial populations generally increased to pre-spill levels when all
the formaldehyde was removed from the soil.
Only small amounts of formaldehyde were found in the condenser traps or
carbon filters. Radiometric analyses of the sodium hydroxide bubblers indicated
that the majority of the formaldehyde was metabolized to C02- No residual was
found in the soil. Thus, it appears that metabolism of the formaldehyde was
performed by methylotrophic bacteria probably utilizing the alternate ribulose-
5-phosphate pathway suggested by Colby and Zatman and reported in Anthony (1975).
For the aniline spill, the initial soil treatments with primary sewage
effluent were ineffective in accelerating the removal of aniline from the soil.
However, enhanced degradation of aniline was achieved when a mixed microbial
culture, grown in the presence of aniline with nutrient salts and yeast extract,
was added to the soil. The addition of the mixed culture increased the rate of
disappearance of aniline from the organic and sandy soil treated chambers.
The use of adapted microbial cultures to degrade the environmentally
persistent compounds, chlordane and dinitrobenzene in situ, were studied as the
third land restoration method. Due to contract time constraints, these chemicals
were only monitored for 49-62 days after the spill. In the chlordane spill,
significant 1^C02 levels were not detected in NaOH bubblers indicating that
cleavage of the rings did not occur. However, some loss of chlordane was observed
in some of the treated chambers The data on the dimtrophenol spill indicated
that some increase in the rate of disappearance of dimtrophenol did occur in the
organic and clay soils treated with adapted microbial cultures. However, since
this compound was not radiolabe 1 led, it is uncertain if the disappearance was due
to the biodegradation or simply biotransformation of the compound
The uptake of cadmium and lead from the soil by plants was evaluated in
Technique IV. The results indicated that the plants concentrated the highest
amount of metal from the soils which received a chelating agent, disodium EDTA.
The plants also concentrated cadmium to a greater extent than lead.
4
-------
The data indicate that uptake of metals by plants can provide an effective
method of removing the metals from the soil. Proper soil conditions must be
maintained to aid the uptake, e.g., acidic pH and the presence of a chelating
agent. In addition, at least several harvests of the plants would have to be
conducted. Although not evaluated in this study, plant uptake of certain
persistent organics from the soil should also be feasible
The accelerated removal of formaldehyde and aniline from the soils in
Technique II and the uptake of cadmium by the plants were the most successful
results. These techniques should be further evaluated for the chemical tested
and possibly expanded to other hazardous chemical classes.
5
-------
SECTION 3
RECOMMENDATIONS
The treatment of hazardous spill-damaged lands cannot be effective until
laws are enacted to require the reporting of all significant spills of all
hazardous materials. Currently, partial reporting of spills to the U.S. EPA,
state EPA and other state agencies occurs. The Department of Transportation also
receives spill reports, but these may be delivered months after the spill occurs
No one group has complete records on the magnitude of hazardous material spills
on land.
Once a coordinated communication system is developed, recommended pro-
cedures for the treatment of chemicals or classes of chemicals should be
developed more completely. Manufacturers, shippers, state and federal agencies
should meet for an exchange of information and cooperation in the treatment of
spills. Areas where information is lacking could be identified and goals
formulated.
Future research and development efforts on restoration of spill damaged
lands should concentrate on the following areas1
demonstration of vn situ biodegradation of chemicals that
can easily be degraded by microbes and preparation of a
detailed guide for the application of this technology by
the on-site spill response coordinator
- demonstration of vegetative uptake of metals from the soil
and preparation of a detailed guide for the application of
this technique to actual spill situations
research on the uptake of persistent organics by plants
research into adapted/mutant or genetically engineered
microorganisms to degrade specific environmentally
persistent chemicals such as the polyhalogenated organics
research on the application of photochemical degradation
to a land spill of persistent polyhalogenated organics
6
-------
SECTION 4
LITERATURE REVIEW OF HAZARDOUS SPILLS ON LAND
AND RESTORATION METHODS EMPLOYED
IDENTIFICATION OF HAZARDOUS SPILLS ON LAND
Under Pl-95-500, it is not mandatory to report hazardous spills on land
when surface water is not threatened. As a result, the data on spills of
hazardous materials on land are limited. However, the Office of Hazardous
Materials of the Department of Transportation (DOT) maintains computer files and
reports on hazardous material spills occurring during transit. These files were
examined for the years 1971-1978 to identify large spills of hazardous materials
on land. Computer printouts contained information on the commodity or chemical
spilled, locations of the spill, shipper and cause of the spill. Reports
concerning spills of the 271 hazardous substances listed in Federal Register,
Vol. 43 (49), p. 10474, were then evaluated by the following criteria:
size of the spill
locations of the spill
methods used for clean-up
A partial list of spill reports which were selected for further analysis is
presented in Table 1 During the evaluation, it was noted that large, common
spills were mainly acids and bases. Smaller spills of unusual chemicals, such as
styrene monomer, were also examined.
The U.S. EPA Regional Offices spill response units having jurisdiction for
each spill were contacted for additional information. Reports on the actions
taken by the U S. EPA or the names of responsible individuals at the state level
were obtained. A large number of spills reported to DOT were not reported to, or
received no action from the U.S. EPA. State and local agencies contacted for
information on the spills included the state EPA, Department of Natural
Resources, Department of Agriculture, State Police, the County Sheriff, and
state laboratories. Reports on the response to the spills, chemical data, and
other pertinent information were received. Many spills had received no response
at the state level or little information was available on the spills. Other
sources were contacted for general and specific information on the spills These
sources included shippers, carriers, contracted laboratories, Chemtrec (on-line
emergency chemical information system) and the EPA data base (OHM-TADS)
A final group of spills was selected for detailed analysis. They were
chosen based on the chemical spilled, the information available, location, and
7
-------
TABLE 1. LAND SPILLS OF THE 271 HAZARDOUS CHEMICALS 1971-1977
State/City
Date
Chemical
Amount Spilled
How Spilled
AL
Wilcox
5/11/76
Aniline Oil
11,356
liters
derailment
AZ
Peridot
5/20/77
Sulphuric Acid
11,848
kg
accident
AR
Spadra
1/08/76
Acetic Anhydride
283,906
1lters
derailment
AR
Wave land
7/02/78
Cyclohexane
68,137
1lters
derailment
AR
Pine Bluff
2/03/77
Caustic Potash
Tank car
rupture
CA
LaMirada
5/08/78
Vinyl Acetate
3,785
1 iters
rail leak
CA
Pinole
8/04/78
Sodium Hydroxide
101,070.
liters
accident
CA
Union City
1/25/77
Calcium Hypochlorite
317
kg
leak
CA
Los Angeles
11/08/77
Ferric Chloride
83
drums
leak
CO
Steamboat Springs
10/21/77
Anhydrous Ammonia
2,041
kg
accident
FL
Balm
7/07/77
Phosphoric Acid
72,907
1iters
accident
FL
St Petersburg
1/13/78
Chlorine
109
kg
unload
FL
Wildwood
2/18/78
Phosphoric Acid
92,396
kg
derailment
FL
Youngstown
2/26/78
Chlorine
40,823
kg
derailment
GA
Dub 1 in
7/08/77
Calcium Hypochlorite
19,169
kg
accident
GA
Augusta
1/16/77
Muriatic Acid
9,463
liters
accident
IL
Centerville
5/29/76
Chlorosulfonic Acid
24,302
liters
derailment
IL
Chicago Heights
5/31/77
Hydrochloric Acid
10,221
licers
derailment
IL
Crescent City
10/10/77
Muriatic Acid
11,356
1 iters
accident
IL
Davis Junction
3/31/77
Phosphoric Acid
32,176
1 iters
derailment
(MTL 69% Fert)
IL
Stoy
5/29/76
Sulphuric Acid
49,487
liters
derailment
IN
Belleville
2/17/78
Phosphorus Pentasulfide
907
kg
accident
IN
Ligoneer
5/08/71
Lead Arsenate
86
kg
accident
(continued)
-------
TABLE 1 (continued)
State/City
Da te
Chemica 1
Amount Spilled
How Spilled
KA
WichiCa
6/07/77
Toluene
507
liters
leak
KY
Benson
12/07/77
Acrylonitrile
26,498
1i ters
derailment
KY
Leon
1/30/78
Acrylonitrile
389,897
liters
derailment
KY
Louisville
10/18/77
Trlme thylamine
189
liters
rail leak
KY
Louisville
9/27/76
Nitric Acid
7,076
kg
accident
KY
Russe11
2/01/78
Butyl Acetate
38,971
liters
rail leak
LA
Avondale
2/02/78
Formaldehyde
757
liters
derailment
MD
Slabtown
6/27/72
Phenol
94,635
1lters
derailment
MA
Deerfleld
12/03/77
Sodium Hydroxide
5,678
liters
leak
MN
St Paul
7/25/74
Chlordane
37
liters
leak
HO
Cla rksvi1le
8/19/77
Acetic Acid
9,822
kg
leak
MO
Itanniba 1
4/20/78
Monochlorobenzene
189
1 iters
derailment
MO
Lamar
12/16/76
Ethylene Dichloride
3,785
liters
accident
MO
Needles
1/19/77
Toluene
49,210
1iters
derailment
MS
Brohman
2/04/78
Phenol
83,279
liters
derailment
MS
Duffee
7/04/77
Caustic Soda
60,566
1 iters
derailment
MS
Duffee
7/05/77
Caustic Soda
5,678
liters
derailment
MS
Sebastopol
2/09/77
Sulphuric Acid
41,730
kg
derailment
MS
Yazoo City
6/22/77
Insectic i de
Various
accident
MT
Whitefish
12/15/77
Sodium Hydroxide
1,950
kg
rail leak
NC
Addor
12/13/76
Acetic Acid
78,297
liters
derailment
NC
Char lot te
11/23/76
Styrene Monomer
189
1 iters
leak
NC
Charlot te
1/28/77
Acetic Acid
18,688
kg
acc ident
(continued)
-------
TABLE 1 (continued)
Sta te/City
Date
Chemica1
Amount Spilled
How Spilled
NC
Clarkton
8/04/77
Chromic Acid Solid
90
kg
derailment
NC
Hamlet
1/06/76
Toluene
5,678
kg
accident
NC
Sliver City
8/23/78
Toluene
7,571
1 iters
accident
NC
S Rocky Mtns.
6/24/78
Phosphoric Acid
725,748
kg
derailment
NE
Hastings
8/02/76
Phosphoric Acid
90,968
kg
derailment
NJ
Jersey City
2/07/77
Chlorobenzene
208
1 iters
leak
NJ
Ma tawan
5/19/77
Toluene
2,900
liters
leak
NJ
Metuchen
6/22/77
Caustic Potash
78,278
kg
derailment
NM
Tucumcari
3/26/76
Parathion
45
kg
leak
NY
Brooklyn
2/07/73
Zinc Cyanide
91
liters
leak
NY
E Shohola
11/07/76
Acetaldehyde
112,502
liters
derailment
NY
Pouglikeeps le
2/06/76
Muriatic Acid
26,498
liters
dera ilment
NY
Rensselear
6/06/72
Formaldehyde
18,927
liters
accident
NY
Syosset
3/29/77
Nitric Acid
1,136
liters
leak
Oil
Apco
12/23/77
Acetic Acid
37,854
liters
derailment
OH
Ashtabula
11/04/77
Caustic Potash
37,854
liters
puncture
Oil
Bellevue
2/08/78
Caustic Potash
5,216
liters
rail leak
Oil
Cincinna t i
4/17/77
Hydrochloric Acid
17,034
liters
derailment
OH
Dayton
6/11/74
Acrylonitnle
31,642
1iters
derailment
Oil
Hanover
1/22/77
Ethyl Acrylate, Ethylene
227,125
liters
dera ilment
Oxide, Acetaldehyde
total
Oil
Kingsvi1le
8/25/78
Phosphorus Trichloride
14,519
kg
accident
Oil
Koppers
1/26/78
Phenol
5,648
liters
unload
OH
NorLhfield
10/20/76
Ma lath ion
189
1 iters
leak
OK
Goultry
8/05/77
Ammonia
2, 721
kg
leak
OK
Kingfisher
4/16/77
Hydrochloric Acid
34
1iters
accident
(continued)
-------
TABLE 1 (continued)
State/City
Date
Chemical
Amount Spilled
How Spilled
OR
Hmkle
4/07/78
Phosphoric Acid
91,580
kg
rail accident
PA
Jim Thorpe
10/29/77
Caustic Soda
3,785
liters
derailment
PA
Marshall Creek
1/07/77
Cyanide Compound
20
1iters
accident
PA
Pond Eddy
1/14/78
Acetaldehyde
103,720
1 iters
derailment
PA
Spring City
3/01/77
Chlorobenzene
208
1 iters
leak
PA
Trainer
2/16/76
Carbon Bisulfide
5,004
1 iters
derailment
SC
Estill
8/04/77
Nitric Acid
3,592
kg
accident
TN
Bean Sta .
8/21/78
Propionic Acid
15,899
liters
accident
TN
Kings ton
3/05/73
PCB
5,678
liters
acc ident
TX
Andrews
12/15/76
Hydrochloric Acid
17,034
1lters
accident
TX
Canyon
11/22/78
Cyclohexane
3,028
1 iters
derailment
TX
Hourd
9/27/77
Hydrochloric Acid
2,839
liters
accident
TX
Houston
5/28/77
Sulfuric Acid
1,136
1 iters
accident
TX
Houston
11/22/77
Sulfuric Acid
708
kg
accident
TX
Justin
3/09/78
Butyl Acetate
76,545
1 iters
derailment
TX
Luffins
10/20/77
Hydrochloric Acid
7,571
liters
accident
TX
Port Allen
8/05/77
Sulfuric Acid
15,086
kg
accident
TX
Weimar
3/12/78
Ana 1ine
2,271
1 iters
rail leak
TX
Westhoff
7/01/76
Monoethanolamine
17,391
kg
accident
UT
Ilolden
8/17/77
Benzol
5,867
liters
accident
UT
Wa 1lsburg
6/17/77
Toluene
14,146
liters
accident
VA
Roanoke
7/29/75
Toluene
14,309
liters
accident
WA
Humorist
10/08/77
Phosphoric Acid
113,562
1 iters
derailment
UA
Pullman
9/05/77
Ammonia
11,356
1iters
leak
(continued)
-------
TABLE 1 (continued)
Scate/Ci-ty
Dace
Chemical
Amount Spilled
How Spilled
WI
Cameron
11/15/78
Xylene
10,410
1 iters
accident
WI
Elkhorn
7/30/77
Arsenic Trioxide
8,582
kg
derailment
WI
Milwaukee
2/24/78
Ethyl Benzene
38,675
liters
rail rupture
WV
Gauley Bridge
5/19/76
Methyl Methacrylate
18,262
kg
accident
WV
Kroy
4/21/78
Nitrobenzen
189
liters
derailment
WV
Orleans Rd
11/28/77
Ammonia
121,133
liters
derailment
WV
Sandstone
1/15/76
Acrylonitrile
151,416
liters
derailment
-------
techniques used to treat the damaged areas These spills and the methods
employed to restore the damaged lands are discussed in detail in the following
sections.
PCB SPILL, KINGSTON, TENNESSEE
Background of Spill
On March 5, 1973, a truck accident and spill occurred on Highway 58 near
Kingston, Tennessee. Details of the spill are presented in Table 2. The
material spilled was composed of polychlorinated biphenyls (Aroclor 1254) and a
proprietary solvent mixture of polychlorinated benzenes. The spill occurred on
land which was used as pasture. The spill site was in a water shed approximately
1 km long which drained into a lake (Figure 1). In addition, it was found that
the spill migrated across the road affecting a second watershed.
The rural area affected had several houses which received their drinking
water from wells at, or near, the contaminated watershed. When heavy rains fell
at the site, distributing the PCBs horizontally and vertically in the soil, a
massive clean-up of the area was initiated.
Climate of Spill Area
Average weather conditions for the spill site from 1942-1970 are presented
in Table 3. East-Central Tennessee receives the greatest amount of rainfall
from December to March. The high wind months overlap with the high precipi-
tation months, occurring from February through April and averaging near 15 kmph
(9 mph) from the northeast. The PCB spill occurred during the time of above
average wind and precipitation levels The precipitation data for the 1973-1975
is presented in Table 4. In March, 1973,when the spill occurred, 32 cm (12.44
inches) of rain fell in the area, 19 cm (7.61 inches) above the average. Heavy
rainfall was also reported in the following three months: April to June. These
three months had a combined rainfall 24.5 cm (9 65 inches) above the normal
levels The heavy precipitation in the spill area increased the hazards from
the spilled Aroclor 1254.
Geology of Spill Area
Moein (1976) studied the geological features of the spill site. "The
geological formations of the site area strike 40° northeasterly on the average,
and normal dips are 25-35° to the southeast. The rocks underlying the total
spill area are part of the Knox dolomite group A shaley limestone series known
as the Chickamauga formation lies to the southeast and upon the Knox group The
Knox of the area is the usual sequence of thin to massive-bedded dolomite (high
MgC03 as compared to limestone with its high CaCOj) and is well fractured
The overburden above the Knox group is thick—in the 15.2 to 45.6 m range.
The primary overburden is made up of clays mixed heavily with chert fragments
On top of the clay is a zone of top soil ranging from 0 to 122 cm in thickness
The top soil allows for ease of percolation while the clays are penetrable
primarily through the fracture crevices of the chert "
13
-------
TABLE 2. BACKGROUND OF PCB SPILL
KINGSTON, TENNESSEE
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
Askarel, Aroclor 1254 (PCB)
5,678 liters
Truck accident
March 5, 1973
Kingston, Tennessee
A1 J Smith
EPA
Region IV
Atlanta, Georgia
data not available
14
-------
^'-MjSsK:
m^yp
^'l\'v/L
7A'WtiVf~0-<^.
CONTOUR INTltVAL TO PEET
OASHEO LINES RCPNESCNI h»l? |MI«W»L CONICURS
OitUM IS MC»» St» LEVEL
Figure 1. Topography of spill site, Kingston, Tennessee
(Moein, 1976).
15
-------
TABLE 3 WEATHER CONDITIONS - KINGSTON, TENNESSEE AREA
(RUFFNER AND BLAIR, 1978)
Month
Average
Temperature
°C (°F)
Average
Precipitation
cm (inches)
Average
Wind Speed
kmph (mph)
January
4.7
(40.5)
11.6
(4 59)
13.1
(8.2)
NE
February
5.8
(42.5)
12.0
(4.73)
13.9
(8.7)
NE
March
9.6
(49.4)
12.2
(4.83)
14.7
(9.2)
NE
April
15.0
(59 0)
9.2
(3.64)
14.7
(9.2)
NE
May
19 6
(67 4)
9.0
(3.58)
11.6
(7.3)
SW
June
24.3
(75.8)
8.8
(3.47)
10.7
(6.7)
SW
July
25 7
(78.4)
12.0
(4.72)
10.0
(6.3)
S
August
25 0
(77.0)
8.7
(3.43)
9.1
(5.7)
NE
September
22.2
(72.1)
6 4
(2.53)
9.4
(5.9)
NE
October
15.7
(60 3)
6 6
(2 63)
9.2
(5 8)
NE
November
9 1
(48.4)
8.0
(3.15)
11.5
(7.2)
NE
December
5.0
(41.0)
10.8
(4.26)
12 0
(7.6)
NE
Yearly Average
12.3
(54.3)
115.5
(45.51)
11.6
(7.3)
NE
16
-------
TABLE 4. MONTHLY PRECIPITATION LEVELS FROM 1973-1975
AT PCB SPILL AREA (MOEIN, 1976)
Total Precipitation in Centimeters (Inches)
Month
1973* 1974* 1975*
January
11
4
(4.
.51)
25.
,4
(10,
,00)
15.
,0
(5.93)
February
8,
.3
(3.
.30)
13.
.7
(5,
,41)
14.
.9
(5 90)
March
31.
.5
(12.
.44)
9.
,5
(6,
,97)
33.
.5
(13.19)
April
11,
.5
(4.
.55)
8.
,9
(3,
.54)
6.
,2
(2.45)
May
25,
.0
(9.
.82)
18.
,6
(7,
.36)
16.
,3
(6.43)
June
18,
.6
(7.
.33)
6.
,9
(2,
.72)
11
3
(4.47)
July
14,
.7
(5.
.81)
4.
.1
(1
64)
9
2
(3.63)
August
9,
.0
(3.
.58)
13.
.7
(5
.43)
5.
,0
(2 00)
September
11,
.0
(4.
.32)
7.
.8
(3
.10)
13.
, 1
(5 17)
October
8
.0
(3.
.12)
4.
.0
(1
.59)
13.
,2
(5.23)
November
24,
.7
(9.
.74)
10.
.8
(4
.26)
9.
,8
(3.87)
December
21,
.2
(8,
.38)
17,
.8
(7
04)
11
8
(4.65)
*U.S. Department of Commerce, 1973, 1974, 1975.
17
-------
Soil temperatures measured to a depth of 142 cm (56 inches) are presented
in Figure 2. The data indicate a general decrease in temperature with depth, the
largest drop occurring over the first 20-30 cm (8-12 inches). The drainage of
the spill area was in a northeastern direction into a lake .8 km away. Mud of
the spilled material migrated toward the lake.
Response to the Spill
The heavy rainfall during the month of the spill and the geology of the area
increased the chances for possible contamination of two watersheds and several
wells in the spill area. Because of these factors, a large scale removal of the
contaminated soil was initiated on March 14, 1973, nine days after the spill. A
total of 11,531 metal drums of packed soil were removed from the spill site. The
excavated areas were then sealed, backfilled and packed with uncontaminated
soil
Extensive sampling of the water and soil in the spill areas was conducted
by the EPA and Stewart Laboratories, Inc. A follow-up study on the persistence
of the PCBs in the contaminated soil was conducted over the summer of 1975.
Another sampling program is planned for the summer of 1979.
Environmental Levels of Spilled Material
PCB levels in the soil are presented in Table 5. PCBs were found at depths
of over 1.5 meters in 1973. Comparing the PCB levels in the soil samples
collected in 1973 and 1975 revealed that the distribution in the clay soil was
non-uniform. This was due in part of "hot spots" along root systems and through
fractured chert found in the clay matrix (Moein et al., 1976).
Further analysis of the PCBs found in the soil in 1975 indicated the same
distribution of chlorines per biphenyl as found in 1973. No PCB degradation
products were found in the 1975 soil samples. These two pieces of information
further supported the lack of degradation of PCBs in the soil (Moein et al.,
1976).
PCB levels in water samples collected in 1973 were usually below the 0.5
ppb detection limit. However, two samples, a spring below the spill area and a
well 30 m from the excavation area, had levels greater than 0 5 ppb The highest
level was 2 1 ppb. In 1975, eight wells, a spring and a creek were sampled All
samples were below the 0.5 ppb limit for PCBs (Moein et al., 1976).
The behavior of the polychlorinated benzene solvent was different from the
PCBs. Soil samples collected in 1973 indicated that tetra- and penta-
chlorobenzenes were retained in soil. However, the other parts of the solvent,
mainly trichlorobenzenes, rapidly leached into the ground water. This trend is
illustrated in Figure 3 which shows the solvent levels in a well near the spill
site Shortly after the spill the solvent levels were near 500 ppb. These
levels were reduced to 1 ppb by August, 1975.
18
-------
30.
28.8 -
<£
ce
27.7
26.6 -
25.5 "
24.4 "
23.3
22.2
21.1 h
20
UJ UJ
SOIL TYPE C
SOIL TYPE 3
S0O_IYPE 1
1. REDDISH-BROWN CLAY WIIH CHERT FRAGMENTS
2. YELLOWISH-BROWN CLAY WITH CHERT FRAGMENTS
3. GREYISh-BROWN SHALE TO REDDISH-BROWN CLAY
18.8 "
(M
• rvi
<\J
rsi
f\J
o
O
*—
T"~
o
r-
OJ
fO
r—
rvj
fO
>T
un
O
r^-
00
o
T-
r—
¦
¦
r-
¦
O
A
o
J-
J-
J-
J-
J-
T~
4-
(NJ
1
(NJ
i
0
00
o
o
T—
(\J
ro
DEPTH (cm)
Figure 2. Temperature of three soil types with depth, Kingston, Tennessee
(Moein, 1976).
19
-------
TABLE 5 COMPARISON OF ANALYTICAL DATA FROM CORE SAMPLES COLLECTED IN 1973 AND 1975
(MOEIN et al., 1976)
Collection
Depth Ranges
Analytical Results
—1973
Analytical Results
—1975
Core
Site
Year 1973
Year 1975
PCB Concentration
No. of
PCB Concentration
No of
Identification
(centlmeters)
(mg/kg)
Samples
(mg/kg)
Samples
Part I.
10 cm
Test Cores
RL
22.8- 88.9
48 2- 88.9
1.25-5.87
3
<0.05-14.5
17
UC
22 8-152.4
53 3- 93.9
0.06-0.27
4
<0.05-2.24
16
JF
22.8- 47.5
48.2-129.5
2.04-7.67
3
<0.05-0.36
32
Part II.
10 cm
Core Samples
EK
22.8- 88.9
38.1- 78.7
0.86-2.76
4
<0.05-0 27
4
SR
22.8- 47.5
22.8-104.1
0.27-0.43
3
<0.05-0.89
8
CC
22.8- 91.4
22.8- 63.5
0.88-2.20
3
<0.05-0.40
4
SM
22.8- 91 4
50 8- 91 4
0.44-0.85
3
<0.05-1 10
4
FM
22.8-167.6
88.9-165 1
1.64-3.44
3
<0.05-1.27
8
Part III
40 cm Core Samples
LJ
22.8-109.2
22.8-104.1
0.55-1.45
3
<0.05-7.36
2
MB
22.8- 93.9
22.8- 63.5
1 .60-5.86
3
3.69
1
Kll
22.8- 93.9
53.3- 93.9
4.10-6.56
3
<0.05
1
SW
22.8- 32.5
30.4- 71 1
0.19-1 42
3
23.8
1
JR
22.8 -50.8
22 8- 63.5
0.52-2.40
2
5.00
1
CW
22.8-101.6
22.8- 63.5
0.09-0.29
3
3.23
1
TE
22.8-157.4
22.8- 63 5
0.07-0.21
4
<0.05
1
JD
22.8- 88.9
22.8- 63 5
0.27-0.82
3
0.17
1
MM
22.8-167 6
22 8-185.4
0 23-6.72
4
<0.05-0.27
4
GE
22.8- 88 9
48 2- 88.9
0.68-2.32
3
0.32
1
CT
7.6- 15 2
7 6- 48.2
0.12
1
0.16
1
MT
22.8-101.6
22.8-104.1
1.37-3.00
3
0 89-4 35
2
BT
22.8- 91.4
22.8-104 1
3 44-3 11
3
- 1.34-10 1
2
(continued)
-------
TABLE 5 (continued)
Collection Depth Ranges Analytical Results—1973 Analytical Results—1975
Core Site Year 1973 Year 1975 PCB Concentration No. of PCB Concentration No. of
Identification (centimeters) (mg/kg) Samples (mg/kg) Samples
LP
7.6- 15 2
7 6- 48 2
3 26
1
3.41
1
JS
7.6- 15 2
10.1- 50.8
3.85
1
5.62
1
FA
22.8-106.6
22.8-104 1
1 85-8.50
3
<0.05
2
PT
7 6- 15.2
7.6- 48.2
0 50
1
66.6
1
FO
22 8- 91.4
22.8-104.1
0.05-0.21
3
<0.05
2
AA
15.2- 22.8
7.6- 48.2
0.60
1
0.34
1
EL
22 8-127.0
22 8-104.1
0.11-1.00
3
0 05
2
PS
0.0- 45.7
5.0- 22.8
0.09-0.69
3
2.04
1
DV
22.8- 86 3
22 8- 63 5
0 21-0.58
3
<0.05
1
SS
22.8- 91 4
22.8-104.1
0.46-5.70
3
<0.05
2
HII
22.8-167 6
22.8-104.1
0.05-1.35
3
0
.12-0.67
2
AM
22.8- 96.5
22.8- 63.5
0 09-0.15
3
<0.05
1
VT
7.6- 15.2
0 0- 40.6
0 72
1
0.17
1
JE
47.5- 73.6
47 5- 99.0
0.16-0.20
2
<0.05
1
BA
86.3- 94.0
53 3- 93.9
0.12
1
<0.05
1
TR
83.8-104 1
63.5- 93.9
< 0.05
2
<0.05
1
CV
83.8-132 0
83.8- 47.5
<0.05-1.39
4
<0.05
1
PQ
22 8- 55.8
22.8- 63.5
0.40-0.44
2
0.21
1
MD
0.0- 45.7
7.6- 48.2
0.76-7.50
3
0.15
1
BS
22.8-122.0
25.4-147.3
0 27-15.8
4
0
. 13-7.45
3
HT
22.8-139 7
22.8-104.1
0.13-4.80
4
<0
05-0.16
2
ZZ
22.8-101.6
22.8-104.1
0.47-7.50
3
0
.29-0.50
2
BR
0.0- 45.7
7.6- 48.2
0.63-6.00
3
0 91
1
SL
22.8-155.0
22.8-63.5
0.05-0.20
3
2.05
1
-------
JULIAN DATE - 1974
DAYS AFTER THE SPILL
Figure 3. SoLvent concentration profile - well located closest to PCB spill site (Moein, 1976)
-------
Biological Damage to Area
The spill area was sparsely wooded with pines and hardwoods. Some damage
to trees and shrubs was observed in the area of highest contamintion. No
mammals, reptiles or amphibians were observed in the area By 1975, there was
heavy vegetative growth at the spill site and insects and garter snakes were
noted in the area. Also, earthworms were found in the core samples collected
at the site.
In 1975, microbial data were collected from the soil samples and compared
to pH, soil moisture, soil type and PCB levels The data comparing microbial
counts to pH are presented in Table 6. Bacteria and actinomycete numbers were
highest at pH levels between 4 0-4.5. The effects of moisture content of the
soil on microbial numbers are presented in Table 7 Bacteria and actinomycete
levels were greatest at a soil moisture content between 5-10% The fungi count
was highest at soil moisture levels from 0-5%.
Microbial numbers compared to soil type are presented in Table 8. Only
three of the 11 soil types identified were sampled relatively frequently. Of
these soil types, the yellowish-brown clay had the highest microbial content.
The reddish-brown clay with chert fragments had the lowest numbers of
actinomycetes and fungi. The data comparing PCB levels in the soil with
microbial levels are presented in Table 9. These data indicate no trend
concerning the toxicity of PCBs to microorganisms. Although higher microbial
levels were observed in soil containing PCB levels ranging from .05-5 ppm, other
physical and chemical factors of the soils would have to be considered before
assessing the effects of PCBs on soil or microorganisms.
ACRYLONITRILE SPILL, LEON, KENTUCKY
Background of the Spill
Details of the acrylonitnle spill on January 30, 1978, are presented in
Table 10. Specifically, 4 tank cars of acrylonitnle were involved in a 14-car
derailment. The derailment occurred at the Highway 7 overpass of the C & 0
Railroad near Leon, Kentucky A fire was involved, but was primarily around the
tank cars. A map of the surrounding area is presented in Figure 4. The map
shows that the spill occurred in a rural area near the town of Grayson. A close-
up of the spill area is presented in Figure 5. The acrylonitnle cars were
positioned very close to drainage ditches leading to a river
The derailment occurred about 91 m from the Little Sandy RiveT which is
a water source for Grayson (10 km downstream) and Greenup (67 km downstream).
A drainage ditch and a concrete culvert were dammed to prevent any drainage from
the spill site into the river.
Most of the derailed cars were involved in a fire, the major part of which
occurred near the tracks Of the 390,000 liters of acrylonitrile involved in
the spill, 116,000 liters were recovered and 284,000 liters were lost or burned.
23
-------
TABLE 6. MICROBIAL POPULATIONS RELATIVE TO pH OF
SOIL SAMPLES ( MOEIN, 1976)
Criteriond)
Average Microbiological Counts
Numbers
pH
for
(Per Gram of Soil)
of
Ranges
Average
Bacteria
Actmomycete
Fungi
Samples
4.0-4 5
High
Low
90324
88447
1043
861
4444
4275
49
4.6-5.0
High
Low
215644
215250
1299
1255
2901
2845
66
5.0 Up
High
264315
9970
2426
27
Low
264315
9959
2426
(l)For microbial counts per gram of soil when the number of organisms is
a "less than" number, the high averages are calculated with "less than"
values taken to be positive. The low averages are calculated with the
"less than" values taken to be zero The actual mean of the samples
must lie between the high average and the low average.
24
-------
TABLE 7. MICROBIAL POPULATIONS RELATIVE TO MOISTURE CONTENT OF SOILS
(MOEIN, 1976)
Moisture
(% by Weight)
Criterion^)
for
Average
Average Microbiological
(Per Gram of Soil)
Bacteria Actinomycete
Counts
Fungi
Number
of
Samples
0-5
High
289500
7756
8633
9
Low
289500
7756
8633
t
»—•
O
High
385630
11476
4813
23
Low
385630
11476
4813
10-15
High
236156
1503
2202
32
Low
236156
1503
2202
15-20
High
135940
407
1976
42
Low
135940
407
1976
20-25
High
27240
200
3791
35
Low
27240
200
3791
25-30
High
100000
100
200
1
Low
100000
100
200
^^For microbial counts per gram when the number of organisms is a "less than"
number, the high averages are calculated with "less than" values taken to
be positive The low averages are calculated with the "less than" values
taken to be zero. The actual mean of the samples must lie between the high
average and the low average.
25
-------
TABLE 8. MICROBIAL POPULATIONS RELATIVE TO SOIL TYPES (MOEIN, 1976)
Criterion^) Average Microbiological Counts
for (Per Gram of Soil)
Soil Characteristics
Average
Bacteria
Actinomycete
Fungi
Samples/Soi 1
Reddish-brown clay with chert
High
136628
469
2707
81
fragments
Low
136530
427
2696
Yellowish-brown clay with
High
364796
12557
6093
27
chert fragments
Low
360722
12183
3685
Greyish-brown shale to red-
High
84333
2150
1543
3
dish-brown clay
Low
84333
2150
1543
Reddish-brown clay
High
138667
158
3984
6
Low
138667
125
3984
Greyish-brown siLty clay with
High
207182
723
3127
11
chert fragments
Low
207182
723
3127
Greyish-brown to reddish-brown
High
52375
150
1813
4
silty clay with numerous
Low
52375
100
1813
chert fragments
Greyish-brown to reddish-brown
High
31500
133
1683
3
clay with chert fragments
Low
31500
133
1683
Reddish-brown silty clay with
High
110750
100
4525
2
chert fragments
Low
110750
0
4525
Yellowish-brown silty clay
High
78000
500
1900
1
with chert fragments
Low
78000
500
1900
Greyish-brown clay with chert
High
190333
317
1100
8
fragments
Low
190333
317
1067
Loam (Control)
High
340000
11000
1500
1
Low
340000
11000
1500
The high averages are calculated with "less than" values taken to be positive (<.1 taken as .1).
The low averages are calculated with the "less than" values taken to be zero The actual mean of
the samples must lie between the high average and the low average.
-------
TABLE 9. MICROBIAL POPULATIONS RELATIVE TO PCB CONCENTRATION
IN CORE SAMPLES (MOEIN, 1976)
PCB
Criterion^-)
Average Microbiological
Counts
Number
Concentration
for
(Per
Gram of Soil)
of
(mg/kg soil)
Average
Bacteria
Actinomycete
Fungi
Samples
<.05
High
82825
1066
3378
80
Low
81475
936
3242
.05-5.0
High
273535
5708
3269
55
Low
273353
5643
3249
5.0-10.0
High
920750
1500
4638
4
Low
920750
1475
4638
10 0-30 0
High
140750
375
2700
2
Low
140750
375
2700
30.0-66.6
High
160000
100
750
1
Low
160000
100
750
(l^For microbial counts per gram when the number of organisms is a "less than"
number, the high averages are calculated with "less than" values taken to be
positive The low averages are calculated with the "less than" values taken
to be zero. The actual mean of the samples must lie between the high average
and the low average.
27
-------
TABLE 10. BACKGROUND OF ACRYLONITRILE SPILL NEAR LEON, KENTUCKY
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-Site Spill Coordinator
Ac rylonitrile
Flammable liquid
389,897 liters
(105,991 liters recovered)
Derailment
January 30, 1978
5:53 a.m.
Leon, Kentucky
Allen Bartlett, EPA
Region IV
Atlanta, Georgia
28
-------
CONTOUR INTERVAL 20 FEET
NATIONAL GEODETIC VERTICAL DATUM OF 1929
V
OJXXUNCLC LOCATION
Figure 4. AcryI onitriIe spill near Leon, Kentucky Topography of
area (U.S. Geological Survey, 1978)
29
-------
WOOD
PULP''
<-LEON(~ 1/4 MILE)
RR CULVERT
{S)
- DAM
DRAINAGE
DITCH
CARBON
FILTER
RAMP
o
CONCRETE
CULVERT
DRAINAGE
DITCH
DAM
LITTLE SANDY RIVER
LEGEND: ACN - ACRYLONITRILE
LPG - PROPANE
Figure 5. SpilL site shortly after derailment (Bartlett, 1978).
-------
Climate of Spill Area
The average weather conditions for the Leon, Kentucky area are presented
in Table 11. The spill occurred in late January when frozen soil and snow were
present. January through March have fairly high amounts of precipitation. Also,
winds during the same period are usually greater than 19.4 kmph (11 tnph) and are
from a southerly direction.
Geology of Spill Area
The area has soils of a Muskingreen-Montivalla-Ramsey association.
Response to Spill
The area was evacuated for a two mile radius around the spill, due to the
possibility of toxic fumes. On January 31, the on-site spill coordinator
directed the damming of a drainage ditch and a culvert leading to the
Little Sandy River. It appears that a large amount of the acrylonitrile was in
the soil of the surrounding area. The water supply of Grayson and Greenup were
both shut off the day of the spill.
Because of the danger of contamination of the Little Sandy River, Stewart
Laboratory, Inc., sampled the soil and water from February 4-8 to determine the
acrylonitrile levels. The sampling indicated that the chemical was leaking into
the Little Sandy River and further methods would be needed to treat the spill
site. The C 4 0 Railroad contracted 0 & H Materials to construct 16 aeration
pools to degrade the acrylonitrile. A closed system was constructed. Water from
the contaminated area was treated in the aeration pools and reinjected into the
soil. When the acrylonitrile concentrations in the water were less than 3 ppb,
the effluent was released into the Little Sandy River (Liebenow, personal
communication, 1979).
Environmental Levels of the Spilled Material
The locations of the core samples collected by Stewart Laboratories,
Inc., are shown in Figures 6a and 6b. The positions of the train cars after the
tracks were cleared are also shown in these Figures. Surface soil levels of
acrylonitrile are presented in Table 12. From the soil samples, it appears that
most of the acrylonitrile was located near the tracks or to the south of the
tracks toward Little Sandy River.
More detailed information on soil cores is presented in Table 13. The
cores indicate that acrylonitrile had penetrated the soil to a depth of at least
102 cm. Typical acrylonitrile levels in the Little Sandy River after the spill
ranged from 0.4-0.6 ppm (Stewart Laboratories, Inc., in Bartlett, 1978)
Biological Damage in the Spill Area
Since the spill occurred in winter, biological damage was difficult to
estimate. Some damage could have been produced by the fire after the derailment
31
-------
TABLE 11. WEATHER CONDITIONS, LEON, KENTUCKY
(RUFFNER AND BLAIR, 1978)
Month
Average
Temperature
°C (°F)
Average
Precipitation
cm (inches)
Average
Wind Speed
kmph (tnph)
January
0,
.2
(32.
,5)
11.
.4
(4,
.50)
17.
,6
(11.0)S
February
1
.4
(34.
,5)
8
.8
(3,
.50)
17
9
(11.2)SSW
March
5
.7
(42.
,4)
11,
.3
(4,
.46)
19.
,0
(11,9)SSW
April
11
.6
(52.
.9)
9
.5
(3,
.76)
18
4
(11.5)SSW
May
17
.0
(62.
.6)
9,
.0
(3,
.56)
14
7
(9.2) S
June
22
.3
(72.
.2)
10,
.6
(4,
.21)
13.
.2
(8.3) S
July
24
.2
(75.
.7)
10,
.7
(4,
.25)
11.
.8
(7.4)SSW
August
23,
.5
(74.
,4)
8.
.5
(3,
.37)
11.
.2
(7 .0) S
September
20
.5
(68.
,9)
7,
.1
(2,
.83)
12.
,8
(8.0)S
October
14
0
(57
3)
6,
.1
(2,
,44)
13.
,7
(8.6) S
November
6,
.5
(43.
,8)
8,
.0
(3,
.15)
16.
.9
(10.6)S
December
1
.6
(34.
,9)
9,
.3
(3
68)
17.
.9
(11. 2) S
Yearly Average 12
4
(54.
4)
111,
.0
(43,
.71)
15.
.5
(9.7)
32
-------
39
40
30 LOCATED 58' WEST OF 31
ft CULVERT
CN
CAR
WEIR
RAMP
36
CULVERT
53
LITTLE SANDY RIVER
Figure 6a. Numbered soil sampling locations in spill area west of New Highway 7 (Bartlett, 1978).
-------
1 LOCATED 400' NORTH OF 4
Co
DRAINAGE
m
c>
a:
/ / CULVER
in**
Figure 6b. Numbered Soil sampLing Locations in spill areas (Bartlett, 1978).
-------
TABLE 12. ACRYLONITRILE LEVELS IN SURFACE SOIL SAMPLES1
(STEWART LABORATORIES INC, IN BARTLETT, 1978)
Sample
Acrylonitri le
Sample
Acrylonitrile
Number
levels in ppm
Number
Levels in ppm
1
ND
30
41.6
2
0
31
1,940
3
0
32
14
4
0
33
9.9
5
54
34
20
6
65.9
35
21.3
7
0
36
0
8
60
37
8.1
9
26
38
10 2
10
0
39
0
11
0
40
0
12
0
41
0
13
0
42
0
14
0
43
1,480
15
30
44
4,250
16
0
45
105
17
ND
46
20
18
461
47
1,160
19
ND
48
ND
20
ND
49
ND
21
0
50
ND
22
22
51
ND
23
0
52
20.7
24
0
53
27.3
25
31
54
ND
26
221
55
ND
27
0
56
15,000
28
0
57
340
29
660
58
35.7
59
17.6
^Sample locations in Figures 6a and 6b.
2nd — No data
35
-------
5
6
7
8
8
8
9
9
9
15
22
25
26
30
31
32
32
32
33
33
33
33
34
34
34
35
38
38
38
43
43
43
43
50
51
51
51
51
56
TABLE 13 ACRYLONITRILE LEVELS IN SOIL CORES
(STEWART LABORATORIES INC. IN BARTLETT, 1978)
Soil Samples Percent Acrylonitrile
Soil Depth Soil type Moisture Levels (ppm)
(centimeters) As Received Dry Weight
Surface
ice, disturbed
clay
28 4
54.1
75.6
Surface
moist clay
27.8
47.6
65.9
Core
c lay
20
2
2 5
0-20
sandy
32
60.8
89.9
20-36
clay
25
2
2.7
36-48
clay
24.6
2
22.7
0-18
topsoil
25 4
2
2.7
18-30
clay
19.8
2
2.5
30-41
hard clay
21.0
2
-
0-15
topsoil
20.8
30.0
37.9
0-15
soil core &
oil
35.2
20.0
30.7
Surface
loose soil &
coal
30.8
3.1
4.5
Surface
topsoil
17.2
221.0
274 0
0-8
topsoil
37.8
41.6
66.9
0-10
topsoil
41.6
1,940
3,320
0-13
burned topsoil
20.6
19
23.9
13-25
c lay
25.6
2
2.7
25-36
clay
20.0
2.3
2.9
0-15
top burned
42.4
9.9
17.2
15-28
dark topsoil
27.0
145
199
28-43
top & clay
26 2
1,140
1,350
43-58
clay
19.4
636
789
0-15
top burned
29 8
20
28.5
15-33
dark clay
20.4
67
84.2
33-58
yellow clay
20 0
124
155
Surface
disturbed soil
43.8
21.3
37 9
0-10
frozen soil
27 4
10.2
14 0
10-20
loam
22.0
2
2.5
20-30
loam
20.0
2
2.5
0-13
topsoil
35 4
1,480
2,290
13-25
clay
27.2
165
227
25-36
hard clay
23.6
58
75.9
36-46
hard clay
24.8
40.5
53 9
152-168
liquid at bottom
of hole
11 2
49,300
-
0-30
rich and soil
11.2
282
318
51-69
clay and sand
26.8
2,200
3,010
69-91
gray clay
18 6
744
914
91-102
clay
28.0
38.3
53 2
Surface
disturbed topsoil
29 2
15,000
21,200
36
-------
PHENOL SPILL, SLABTOWN, MARYLAND
Background of Spill
On June 27, 1972, phenol was spilled as a result of derailment of a Western
Maryland Railway freight train. Details of this spill are presented in Table
14. A shift of steel castings in a gondola car caused the 11-car derailment.
Three of the cars were tankers carrying phenol. When the derailment occurred,
two of the tank cars ruptured, spilling 94,635 liters of phenol A topo-
graphical map, in Figure 7, shows the steep contour of the land in the spill
area. The spilled phenol flowed down the steep embankment contaminating a pond,
Trimble Spring, and a creek, Jennings Run, located at the bottom of the hill.
It was estimated that 4,732 liters of phenol initially entered the creek and the
remaining amount seeped into the soil (Ramsey and MacCrum, 1974). A more
detailed illustration of the spill area is presented in Figure 8
Climate of Spill Area
The average weather conditions in the area of Slabtown, Maryland are
presented in Table 15. The wettest months of the year are from May to August,
with about 10 cm of rain per month. The months with the highest winds are
February through April. Weather conditions following the spill are presented
in Table 16 Heavy rainfall occurred on the second and third day after the
spill. The two months following the spill had below average levels of rainfall.
Geology of Spill Area
The soil in the spill area is a Buchannon type or a very stony loam. The
0-18 cm layer is a gravelly loam and 18-24 cm is a gravelly clay loam. The perm-
eability of the soil is 1.5-15 cm/hour. The pH ranges from 5 0-5 5.
Response to the Spill
Shortly after the spill occurred, it was observed that phenol was leaching
out of the soil into Jennings Run. Since Maryland State law prohibits
discharge of toxic substances into waterways, the State required the railroad
to reduce the leaking of phenol into Jennings Run. Several alternatives were
evaluated for treating the spill. Finally, it was decided that the best solution
to the problem would be a carbon filtration system. A trench or collection
channel was made to hold the contaminated runoff from the phenol containing
embankment. A 3.4 m x 3 7 m x 3.4 m box was constructed to hold 4 07 m^
(144 ft^) of gravel and 2.83 m^ (100 ft^) of granular activated carbon. A
gravity flow system was used with the collection channel feeding into the top
of the box and the effluent feeding into Jennings Run. The location of the box
is illustrated in Figure 8
Treatment was initiated during the week of 21 July and excellent removal
of the phenol was accomplished. The activated carbon had to be changed
approximately every 60 days Due to channelization, the filtration system was
modified in the spring of 1973 to feed the influent to the bottom of the
chamber By 17 May 1973, the system was only operated when the phenol levels
37
-------
TABLE 14. BACKGROUND OF PHENOL SPILL, SLABTOWN, MARYLAND
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
data not available
Phenol
Poison B
94,635 liters
Derailment
June 27, 1972
Slabtown, Maryland
W. Lawrence Ramsey
Maryland Water Resources
Administration
Maryland
38
-------
^ Dutch Hollow
SCALE. 124000
¦UtONlTM
CONTOUR INTERVAL 20 FEET MWyumil
NATIONAL GEOOETIC VERTICAL DATUM OF 1929
SUAOMNCU LOCAI.OK
MnMUfl (3 j
Figure 7. Topography of phenol spill area,
(U.S. Geological Survey, 1974).
Slabtown, Maryland
39
-------
SPILL
''SITE
Jd-H-.
TRIMBLE
SPRING -
SLABTOWN RD
TO HT. SAVAGi
SLABTOWN
ENNINGS RU,
TREATMENT BOX
ROAD
POND
SPRING
X
STREAM
INITIAL
Mat
AFFECTIVE AREA
RAILROAD
"HI
SOIL SAMPLES A - E
Figure 8. Detailed map of phenol spill site and sampling
locations (Ramsey and MacCrum, 1974).
UO
-------
TABLE 15. WEATHER CONDITIONS OF SLABTOWN, MARYLAND
(RUFFNER AND BLAIR, 1978)
Average
Average
Average
Temperature
Precipitation
Wind
Speed
Month
°C
(°F)
cm
(inches)
kmph
(mph)
January
-0 6
(30.8)
8.0
(3 16)
12.6
(7 9)WNW
February
-0.3
(31 4)
6 3
(2 50)
17.2
(10.8)NW
March
3.3
(38.1)
10.0
(3.95)
17.9
(11 2)WNW
April
9 8
(49 8)
9.0
(3.57)
17.6
(11 0)WNW
May
15.5
(60.0)
11.0
(4.35)
15.5
(9.7)WNW
June
19.8
(67.8)
11.0
(4.35)
14.0
(8 8 )WNW
July
21.8
(71.3)
9.4
(3 71)
13.1
(8.2 )W
August
21 0
(69.9)
10.3
(4.08)
13.2
(8.3)W
September
17.5
(63.5)
8 1
(3 19)
13.4
(8 4 )S
October
11.8
(53 4)
7.9
(3.13)
14.4
(9.0)NW
November
5.3
(41 7)
6 6
(2 61)
12 1
(7.6)WNW
December
-0.05
(31.9)
7 2
(2 86)
15 2
(9 5 )WNW
Yearly Average
10 4
(50.8)
105.7
(41.64)
15 2
(9 5)W
41
-------
TABLE 16. WEATHER CONDITIONS AFTER THE SPILL IN SLABTOWN, MARYLAND
(RUFFNER AND BLAIR, 1978)
Date
Temperature Range
°C (°F)
Precipitation
cm (inches)
June 27
11.6-26.6
(53-80)
0.0
(0.0)
June 28
13.3-27 2
(56-81)
0.0
(0.0)
June 29
13.3-27.2
(56-81)
3 1
(1.24)
June 30
14.4-29.4
(58-85)
1.6
(0.64)
July 1
14.4-31.1
(58-88)
0.0
(0.0)
July 2
14.4-31 6
(58-89)
0.0
(0 0)
July 3
18.3-31.6
(65-89)
0.07
(0 03)
July 4
15.0-26.1
(59-79)
0.0
(0.0)
July 5
13.3-24.4
(56-76)
1.8
(0.74)
July 6
12 2-20.0
(54-68)
0.1
(0 07)
July 7
8.3-24.4
(47-76)
0.0
(0.0)
July 8
10.5-25.5
(51-78)
0 0
(0.0)
July 9
10.5-27.7
(51-82)
0 0
(0.0)
July 10
14.4-33.8
(58-93)
0.0
(0.0)
June Total
23.9
(9.43)
July Total
5.4
(2.13)
August Total
5.1
(2.02)
42
-------
in the influent exceeded 10 ppm. During the summer cf 1973, low levels of
phenol were found in the influent and on October 3, 1973, the system was shut
dc>vn.
Environmental Levels of the Spilled Material
Phenol levels in Trimble Spring were extremely high. Phenol concentr-
ations for the four days that the spring was sampled were:
Water from Trimble Spring was fed into the collection channel and was treated
by the carbon filtration system.
The effectiveness of the carbon filtration system is illustrated in
Table 17. Initially the system worked very well and removed over 99% of the
phenol from the water. Influent levels, during the first 3 months, ranged from
144-1130 ppm and effluent levels ranged from 0.25-160 ppm. However, channeling
occurred through the filtration system resulting in only 8.6% phenol reduction
on 18 October. The chaneling problem was corrected by reversing the flow and
pumping up through the bottom of the system. By March, 1973, phenol levels in
the influent were less than 60 ppm and by June levels were less than 20 ppm.
Phenol levels in Jennings Run were reduced from 1-2 ppm in October, 1972, to
less than 0.5 ppm in June-August, 1973.
Soil cores were collected on 15 July 1972, and 3 April 1973. The phenol
levels in the soil cores are presented in Table 18. Sample locations are shown
in Figure 8. The initial phenol concentration in the top 17 cm of soil ranged
from 415 to 2757 ppm. Analysis of the soil samples indicated that the phenol had
penetrated the soil to a depth of more than 61 cm. In April, 1973, phenol
levels in the top 17 cm of the soil were reduced to the 30 ppm range. The
reduction of the phenol levels in the soil paralleled the reduced phenol levels
in the influent to the carbon filtration unit
Biological Effects of the Spill
When the phenol spill occurred, all plant life in the spill area was
chemically burned (Ramsey and MacCrum, 1974). It is assumed that the soil
flora would also have been destroyed in the area of the spill. By May, 1973,
the phenol concentration had been reduced to a sufficiently low level that
microbial degradation of the remaining phenol could occur (Ramsey and MacCrum,
1974). Ramsey (personal communication, 1979) stated that after three years the
land area had recovered from the phenol spill
Date
Phenol Levels (ppm)
7/22
8/22
8/28
9/09
1,280
1,500
1,500
1,350
43
-------
TABLE 17. PHENOL LEVELS THROUGH TREATMENT SYSTEM AND JENNINGS RUN (IN PPM)
(NATURAL RESOURCES DEPARTMENT, CUMBERLAND, MARYLAND)
Date Influent Effluent Percent Jennings Run (Downstream)
Removal for an Effluent
7/25
72
144
1 9
98.7
-
7/25
72
156
.25
99.8
-
7/27
72
162
.4
99 8
-
8/01
72
-
8.4
-
-
8/04
72
490
.7
99.9
-
8/08
72
940
5
99.9
-
8/11
72
-
20 0
-
-
8/17
72
740
22.0
97.0
-
8/22
72
740
160.0
78.4
-
8/30
72
500
13.0
97 4
-
10/03
72
850
65.0
92.4
-
10/11
72
1,130
113.0
90 0
-
10/18
72
580
530.0
8.6
2.1
10/27
72
720
-
-
-
10/30
72
580
1.8
99.7
-
11/02
72
1,080
113.0
89.5
-
11/10
72
550
58.8
89.5
1.8
3/05
73
55
60 0
0.0
1.5
3/19
72
25
30.0
0.0
0.7
4/02
73
20
30.0
0.0
.46
4/18
73
30
-
-
.5
4/19
73
30
30.0
0.0
5
5/03
73
26
.1
99.6
.2
5/07
73
15
1 2
92.0
2
5/14
73
7
7 0
0 0
.2
5/21
73
-
7.0
-
.4
5/23
73
-
7.0
-
25
5/25
73
-
7.2
-
.4
5/29
73
11
-
-
3
6/01
73
6
-
-
.3
6/04
73
4
-
-
2
6/08
73
7
-
-
.3
6/11
73
8
-
-
.3
6/15
73
18
8
-
-
42
6/16
73
16
7
95.6
.6
6/20
73
17
5
.7
96.0
3
6/22
73
11
.13
98.8
1
6/25
73
15
8
.6
96.2
.2
6/27
73
16
5
8
95.2
22
6/29
73
21
6
97 1
.38
7/02
73
9
8
91.1
.15
7/06
73
14
.75
94.6
.25
7/09
73
12
.8
93 3
.25
(continued)
44
-------
TABLE 17. (continued)
Date Influent Effluent Percent Jennings Run (Downstream)
Removal for an Effluent
7/11/73
12
.78
93.5
.21
7/13/73
11.5
.7
93.9
.17
7/16/73
9
65
92.8
12
7/23/73
5
.57
88.6
.2
7/30/73
2.3
.8
65.2
.2
8/02/73
6 3
-
-
.5
8/06/73
.5
-
-
.2
8/09/73
1.25
-
-
.27
8/13/73
2.25
-
-
.3
- no analysis
45
-------
TABLE 18. PHENOL LEVELS IN SOIL SAMPLES (NATURAL RESOURCES DEPARTMENT,
CUMBERLAND, MARYLAND)
Phenol Concentrations (ppm)
Location Depth Date Collected Date Collected
cm (inches) 7/15/72 4/3/73
Surface 1.2 1.2
15.0 (6) .9 ND
30 0 (12) 1.4 ND
2 5-17.7 (1-7) 2,727 31.6
25.4-38.1 (10-15) 69 6.8*
40.6-55.8 (16-22) 1.4 9.4*
55.8-71.1 (22-28) 5.4 ND
2.5-17 7 (1-7) 434 32
17.7-30 0 (7-12) 148 59*
40.6-55.8 (16-22) 374 22.8*
60.9-76.2 (24-30) 298 ND
2.5-17.7 (1-7) 415 31.1
17.7-30.0 (7-12) 88 11 0*
30.0-38.1 (12-15) 184 17.0*
45.7-60.9 (18-24) 170 ND
Surface 1.2 16 2
ND 46.3*
ND 37.1*
* Depth not given
ND Not determined
46
-------
ACRYLONITRILE SPILL, DAYTON, OHIO
Background of Spill
On 11 June 1974, a Chessie system freight train was derailed after
hitting an obstruction on the tracks. A tank car containing aerylonitrile was
punctured and caught fire. Details of the spill are summarized in Table 19. A
contour map of the spill area is presented in Figure 9. The spill occurred on
flat land in a relatively low population area.
Climate of Spill Area
The average weather conditions for the Dayton, Ohio area are presented in
Table 20 Typically, the months of March through July have the highest
precipitation. The month of June, when the spill occurred, is typically the
wettest month. The highest winds in the area occur in the late winter and early
spring. The wind direction is primarily from the south-south-west.
Geology of Spill Area
The soil type is a Miamian-celma association with fine textured and well
drained soils. The Fox-Urban land complex soils are well drained and are
underlaid by calcareous sand and gravel at a depth of 61 to 107 cm
(24 to 42 inches). Because of this layer, permeability is rapid and con-
tamination of ground water can occur (USDA, 1976).
The ground at the spill site is underlaid by valley train deposits. The
water table is at a depth of 3-6 m (10-20 feet), overlaid by porous loam and
mixed gravel/clay layers.
Response to Spill
A detailed map of the spill site is presented in Figure 10. The fire
that occurred after the spill, was put out and the area was sprayed to prevent
reignition. Therefore, large pools of acrylonitrile/water mixture were
present in the area.
The day after the spill, 12 June, a pump car arrived to remove the
remaining aerylonitrile from the tank car. About 44,289 liters (11,700
gallons) of the aerylonitrile were recovered. The remaining 31,642 liters
(8,630 gallons) were burned or lost to the environment On 13 June, samples of
the pools of the spilled material were collected and a geologist checked the
site. The results of the tests, as shown below, indicated that very high levels
of aerylonitrile were present in the area:
Puddle north side of tracks
Aerylonitrile Before Treatment
2,203 ppm
Puddle south side of tracks
7,231 ppm
Pool in woods
82-471 ppm
47
-------
TABLE 19. BACKGROUND OF ACRYLONITRILE SPILL DAYTON, OHIO
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
Aerylonitrile
Flammable liquid
31,642 liters
Derailment
June 11, 1974
2:52 p.m
10 kilometers east of
Dayton, Ohio
Mr. Ken Harsh
Ohio EPA
Columbus, Ohio
48
-------
"*00-
fS:
m
!< V ¦'
' V I ; mmh*c
S ¦'« »
A;
•f"'-
0 *
o»««n c
r y*
*Otjr*,*\
'N
V
)
,.. ^ sv ^
r- *"} . A( "...—a-O v
~Jvrr"~~ spill si
II—to. I -- — ^
.< • ¦ I —• _ wi
•ii i
7* ¦","'
/ \i« ,J"--
/ '# i ~MooM
^'""STrrc^o*1
M-i n
/// 0»w*r,,v
r'^RC?
St \. <-'
¦a -L-
SCALE 1 24000
1000 2000 JOOO 4000 5000 6000 7000 FCCT
I KILOMETER
CONTOUR INTERVAL 10 FEET
NATIONAL GEODETIC VERTICAL DATUM of 1929
OUAOHANGLE t-OCAftO*
Figure 9. Topography of acryIonitrite spill area, Dayton
Ohio (U.S. Geological Survey, 1974)
49
-------
TABLE 20. WEATHER CONDITIONS, DAYTON, OHIO
(RUFFNER AND BLAIR, 1978)
Average Average Average
Temperature Precipitation Wind Speed
Month °C (°F) cm (inches) kmph (mph)
January
-1.2
(29.7)
7.5
(2.96)
18.8
(11.8)
S
February
-0.3
(31.4)
5.3
(2.11)
19.3
(12 1)
WNW
March
4.3
(39.8)
8.2
(3.24)
19.8
(12.4)
WNW
April
10.2
(50.5)
7 7
(3.07)
19.2
(12.0)
SSW
May
16.1
(61.0)
8 9
(3.54)
16.1
(10.1)
SSW
June
21.6
(70 9)
9.9
(3.90)
14.5
(9.1)
SSW
July
23.8
(75.0)
8.3
(3.29)
12 8
(8.0)
SSW
August
22.7
(72.9)
7.2
(2.86)
12.0
(7.5)
SSW
September
19.3
(66.9)
7 1
(2.80)
13.2
(8.3)
SSW
October
12.8
(55.1)
5.8
(2.30)
14 4
(9.0)
SSW
November
5.5
(41.9)
6.6
(2 61)
18.2
(11.4)
S
December
-0.1
(31.7)
6 2
(2 47)
18.4
(11.5)
SSW
Yearly Average
11 2
(52.2)
89.2
(35.15)
16.4
(10.3)
50
-------
/
N
^ POOL
TANK CAR
RESIDENCES.
GOLF COURSE
CONTAMINATED AREA S. OF TRACKS
\
RESIDENCES
SCALE 1" = 33.1 METERS
Figure 10. Detailed map of spill site (Harsh, 1978).
-------
It was determined that the spill presented a danger to the ground water supply
in the area (Harsh, 1978).
The Ohio EPA decided to oxidize the acrylonitrile on site. This process
was accomplished first by raising the pH above 10 with lime and then spraying
sodium hypochlorite over the area. According to the reaction.
(1) CN" + HOC1+CNC1 + OH"
(2) CNC1 + 20H"¦* CNO" + CI" + H20
(3) 2CNO" + 30C1" + H20 ¦+ 2C02 + N2 + 3C1" + 20H"
On 15 June, 4,354 kg (9,600 pounds) of lime were applied to the
contaminated areas and 635 kg (1,400 pounds) of sodium hypochlorite were
sprayed on the areas by 0 & H Materials. Results of the treatment are shown
below
Acrylonitrile
After Treatment
Percent
Removal
Puddle north side
of
tracks
62.5 ppm
97.1
Puddle south side
of
tracks
13.1 ppm
99.8
Pool in woods
24.0 ppm
90-96
The percent removal in the highly contaminated area was 97% or greater.
Overall, acrylonitrile levels were reduced to the 13-63 ppm range.
Environmental Levels of Spill Material
Although the surface pools were heavily contaminated before clean-up,
water samples of the wells in the area indicated no contamination of the water
table.
Biological Damage to Area
Most of the damage to plants in the area was due to the fire No other
effects were noted (Harsh, personal communication, 1979).
NITRIC ACID SPILL, ESTILL, SOUTH CAROLINA
Background of Spill
In Estill, near the intersection of Route 3 and Route 321, there is a
railroad crossing. On August 4, 1977, a truck carrying nitric acid was
crossing the railroad tracks. While on the tracks, the driver noted a switch
engine coming toward his trailer The engine hit the end of the trailer,
overturning the trailer Details of the spill are presented in Table 21 A
contour map of the spill area is shown in Figure 11.
52
-------
TABLE 21. BACKGROUND OF NITRIC ACID SPILL ESTILL, SOUTH CAROLINA
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
Nitric Acid
Corrosive Material
3,592.4 kg
Truck-train accident
August 4, 1977
3:00 p.m.
Estill, South Carolina
Marshall Dixon and
Karl Chandler
South Carolina Department of
Health and Environmental Control
53
-------
•SPILL SITE
^k; jpi Fjfiai o
. ritJ-''««"•*¦
M.U-*
Contour ukii'ivni lO litl
IS 'ONfi «
-------
Climate of Spill Area
The average weather conditions in Estill, South Carolina, are presented in
Table 22 The month of the spill, August, is one of the wettest months of the
year, with an average precipitation of 16 5 cm (6 49 inches). Winds, from March
through August, are from the south and south-west. During the winter months, the
winds are predominantly from the north and north-west.
Geology of Spill Area
The soil characteristics of the area are typically a Ruston sandy loam. The
top soil has an average depth of 15 cm (6 inches) and is a gray to gray-brown sandy
loam. The subsoil has a depth range from 38-61 cm (15-24 inches) and is made up
of a reddish-yellow sandy loam and a reddish- yellow clay (Whitney, 1915).
Response to Spill
The on-site coordinators (OSC) arrived at the scene at 5'00 p.m , two hours
after the spill. They found the tanker on its side leaking nitric acid from a
pipe in the top of the tank. The fire department had been spraying water on the
acid since 3:15 pm. The water/acid mixture was flowing into a drainage ditch
along the tracks. The OSC had the ditch dammed to limit the soil contamination
At midnight, the trailer was righted and two truckloads of lime were applied to
the road and in the ditch.
Clean-up operations were started the next morning, 5 August. The upper 10
cm (4 inches) of topsoil were removed and deposited in the ditch so the
contaminated water and soil could be uniformly neutralized with lime. The dirt
was then hauled to a landfill. Forty to fifty truck loads were required to
remove the soil Forty-two truck loads of clean soil were used to fill in the
spill area. The soil was then graded and reseeded. The cost of the clean-up was
approximately $5,300.
Environmental Levels of Spilled Material
The trailer was leaking 67% nitric acid. The only measurement in the spill
area was the acid/water mixture in the ditch The pH of that mixture was 1 8.
Biological Damage to Area
Due to the low pH of acid/water mixture, all plant life in the spill area was
chemically burned. Soil fauna in contact with the chemical were also chemically
burned.
CAUSTIC SODA SPILL, DUFFEE, MISSISSIPPI
Background of Spill
An Illinois Central Gulf railroad train was involved in a 12-car derailment
in Duffee, Mississippi on July 4, 1977 One car containing caustic soda ruptured
when the derailment occurred, releasing its contents, 60,567 liters (16,000
gallons). Another car, also containing caustic soda lost 5,678 liters (1,500
55
-------
TABLE 22 WEATHER CONDITIONS, ESTILL, SOUTH CAROLINA
(RUFFNER AND BLAIR, 1978)
Average Average Average
Temperature Precipitation Wind Speed
. Month °C (°F) cm (inches) kmph (mph)
January
10.3
(50.6)
6 5
(2.57)
14.7
(9.2)
SW
February
11.1
(52 0)
8 8
(3.49)
16.4
(10.3)
NNE
March
14.1
(57.4)
9.8
(3 87)
16.6
(10.4)
SSW
April
18.4
(65.2)
8.6
(3.41)
16.1
(10.1)
SSW
May
22.5
(72.6)
9.6
(3.78)
14.2
(8.9)
S
June
26.0
(78.9)
13.0
(5.15)
13.6
(8.5)
S
July
27.0
(80.7)
17.2
(6.78)
12.8
(8.0)
SW
August
26.8
(80.3)
16 4
(6.49)
11.8
(7 4)
SW
September
24.4
(76 0)
11 4
(4.49)
12.8
(8.0)
NNE
October
19.1
(66.5)
7.4
(2.92)
12.9
(8.1)
NNE
November
13.6
(56.6)
5 7
(2.25)
13.1
(8.2)
N
December
10.0
(50.0)
6.9
(2.74)
13.9
(8 7)
NNE
:arly Average
18.6
(65.6)
123.0
(48.44)
14 0
(8.8)
56
-------
gallons) when rerailing of the car was in progress. Details of the spill are
presented in Table 23. A contour map, with the location of the spill is presented
in Figure 12.
Climate of Spill Area
The weather conditions for the Duffee, Mississippi area are presented in
Table 24. Although the greatest precipitation of the year occurs during the
winter months, July, the month of the spill, also had high amounts of rainfall.
Average wind speeds during the summer months range from 9.7-11 kmph (5 8-6.7
mph).
Geology of Spill Area
The soil is a bibb type. These soils are on flood plains and are poorly
drained, strongly acid silt loam or sandy loam soils. The pH is 5 1-5.5 and the
permeability is 2-6.2 cm (0.8-2.50 inches)/hour (USDA, 1960).
Response to Spill
Initially, the railroad treated the spill site by flushing with water and
removing the soil to a disposal pit (Dickson, personal communication, 1977).
Since no water bodies were affected, the railroad did not treat the area further.
However, one month later, the railroad was notified of resident complaints
of fumes and high pH water. They were instructed by the Mississippi Air and Water
Pollution Control Commission to further treat the spill site in early August.
The railroad applied 2,721 kg (6,000 pounds) of alum to reduce the pH of the soil.
Environmental Levels of Spilled Material
After treatment with alum, soil pH levels were measured in the spill area
(Table 25). The pH levels indicated that the treatment was fairly successful in
reducing the high pH
Biological Damage to Area
Harper (personal communication, 1977) noted that damage to vegetation and
drainage contours had occurred. It is probable that soil fauna were also removed
from the spill area. However, upon lowering of the pH, recolonization of the area
should occur
FORMALIN SPILL, RENSSELAER COUNTY, NEW YORK
Background of Spill
Details of the spill are presented in Table 26. On June 6, 1972, a tire blew
out on a chemical truck in Rensselaer County, New York. The truck rolled down a
25 foot embankment and ruptured spilling 18,927 liters (5,000 gallons) of 40%
formaldehyde solution The spill occurred on a hill in the median of the highway
several hundred feet from a stream The stream feeds into Roundtop Pond. A
contour map of the area and a detailed map of the spill site are presented in
Figures 13 and 14
57
-------
TABLE 23. BACKGROUND OF CAUSTIC SODA SPILL DUFFEE, MISSISSIPPI
Chemical Spilled
Class of Material
Amount Spilled
How occurred
Date
Time
Location
On-site Spill Coordinator
Liquid caustic soda - NaOH
Corrosive material
66,244.7 liters
Derailment
July 4, 1977
3:10 a.m.
Duffee, Mississippi
John W. Harper
Air and Water Pollution Control
Commission
Jackson, Mississippi
58
-------
^ ..UVftyO f; j b C -
fij i S !) \ . . ,*>$
.J - X -• ' '; \ S lr* *> .tu V.V '
-v r i J < ¦<
yTTTHgSS-J '-•-> l&
w
"' ' '*?* ** SPILL SITE
-•• : '"hv i : :a , • ,*>
-'1 ^r.' \*\ / / t1 I „¦ 4r
"t ^ \,"-^ c s *slv~LC ;
.-,/v i-\ J'S<. . /* xM x' ^Z
_ • ^ - sk^ * / J8 - .•;.":^/4"
. ^<5 A' C* ' \| V / ^j3 "'-« '
>rv^s i!i
. -kk;r ^ ^ Jl_ .:;*#? 3v
\ " ^ 1 ~ -^:;V 3 ^ \ ' ' i
• • -i
+ V • N
i ^ , t>-_c
Y> 5 . [ '>- -J : 'ftwidenet' ' V' "" '
^ip- • %A
¦J «Jj5 \ ' **4+ ' X ', '3*1 '
¦CK-^rJ '/j' ^ > K4 » nA {¦£T >
• J ->\ . " " c b iv lio^v
' 13 i \\t'7
A • 'ro
' o
A'
^ "Vn
SCALE 1 62500
5 KttOMCTflU
4
>1000 rcn
CONTOUR If.TERVAt 2C FEET
OaT,;m IS yiAN Sf A tC-.EL
-------
TABLE 24 WEATHER CONDITIONS, DUFFEE, MISSISSIPPI
(RUFFNER AND BLAIR, 1978)
Month
Average
Temperature
°C (°F)
Average Average
Precipitation Wind Speed
cm (inches) kmph (mph)
January
9.3
(48 9)
14.0
(5.53)
14.5
(9.1)
February
10.5
(50.9)
12.2
(4.84)
14.5
(9.1)
March
14.0
(57.3)
15.0
(5 93)
15.3
(9.6)
April
18.0
(64 5)
11 3
(4 47)
14.7
(9.2)
May
22.2
(72.1)
10.2
(4 03)
11 8
(7.4)
June
26.3
(79.4)
8.8
(3.47)
10.0
(6.3)
July
27.5
(81.5)
12.8
(5.05)
9.9
(6.2)
August
27.3
(81.3)
7.6
(3.00)
9.2
(5 8)
September
24.5
(76.1)
4.9
(1 93)
10 7
(6.7)
October
18.9
(66.1)
4.3
(1 70)
10.5
(6 6)
November
12 6
(54.8)
8.7
(3 43)
12.6
(7.9)
December
9.7
(49.5)
14.0
(5.54)
13.9
(8 7)
Yearly Average
18.4
(65 2)
125.6
(49.47)
12 3
(7.7)
60
-------
TABLE 25 SOIL pH LEVELS AFTER TREATMENT WITH ALUM
(DICKERSON, 1977)
Location pH
South of Track 18 3 m from crossing 2.3 n from track 8.1
South of Track 9.1 m from crossing 9.1 m from track 8.1
South of Track 45.7 m from crossing 9.1 m from track 8.2
North of Track 21 3 m from crossing 21 3 m from track 6.8
North of Track 45 7 m from crossing 10.7 m from track 6 8
North of Track 56.4 m from crossing 19.8 m from track 8.9
(over disposal pit)
North of Track 61 m from crossing 9.1 m from track 8.2
61
-------
TABLE 26 BACKGROUND OF FORMALDEHYDE SPILL RENSSELAER COUNTY, NEW YORK
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Location
On-site Spill Coordinator
Formaldehyde
Combustible Liquid
19,000 liters
Tire failure accident
June 6, 1972
Berkshire Section of 1-90,
Rensselaer County, New York
New York State
Health Department
62
-------
:% SPILL SITE
ENSSEXAERJ
^North.
. Chatham-
ciWyqs, _ ¦
2QOO 3000 4CXX? 5000 6000 7QQQ FEET
^—r
SCALE 1:24000
o
I MiLC
CONTOUR INTERVAL 10 FEET J {
OATUM IS MEAN SEA LEVEL /~^wr0,«j
au«0»AN6Lt LOCATION
Figure 13. Topography of formaldehyde spill site, Rensselaer
New York (U.S. Geological Survey, 1971)
63
-------
Climate of Spill Area
The average weather conditions in the spill area are presented in Table 27.
The months of May, June and July receive an above average amount of
precipitation. Winds from May to December are moderate and from the south. The
weather conditions immediately after the spill are summarized in Table 28. June,
1972, was an above average month for precipitation with 17.4 cm (6 84 inches) of
rain. This amount is 9.1 cm (3.59 inches) over the normal amount. Rain occurred
the day of the spill, June 6th, and continued through June 10th.
Geology of Spill Area
The topsoil in the area is a dark-brown silt-loam which persists to a depth
of 18-20 cm (Latimer, 1932). The subsoil is made up of a yellowish-brown sandy
loam. A marsh and stream are located at the bottom of the contaminated slope.
The stream feeds into Roundtop Pond (See Figure 14).
Response to Spill
The formaldehyde was adsorbed by the porous sandy loam soil at the spill
site. Because of the adsorption, no toxic effects of the chemical were noted in
the stream. Treatment or removal of the formaldehyde from the soil was
determined not to be necessary However, the area was monitored for formaldehyde
levels for one year.
Environmental Levels of Spilled Material
Formaldehyde levels in the soil are presented in Table 29. The data
indicate that very high levels of formaldehyde were present at depths of 15-30 cm
(6-12 inches) shortly after the spill. However, three weeks later 80- 90% of the
formaldehyde had evaporated, degraded or was washed deeper into the soil by the
heavy rainfall. One year after the spill, 97-100% of the formaldehyde had been
removed from the top 12 inches of the soil.
In contrast, marsh core sample, data shown in Table 30, indicate increased
formaldehyde levels occurred over time Formaldehyde levels in the ground water
appeared to decrease after the spill (See Table 30). However, after one year,
formaldehyde levels in the water were still relatively high Thus, it appears
that the formaldehyde was moving down the slopes and was slowly leaching into the
creek.
Biological Damage to Area
In the spill area, the formaldehyde killed the plants and most of the
terrestrial invertebrates, such as earthworms and pill bugs. After one year,
plants sucn as clover, sow thistle, and dandelions were migrating into the spill
area. No toxic effects of the formaldehyde were noted on aquatic life in the
creek
64
-------
TABLE 27. WEATHER CONDITIONS, RENSSELAER, NEW YORK
(RUFFNER AND BLAIR, 1978)
Average Average Average
Temperature Precipitation Wind Speed
Month °C (°F) cm (inches) kmph (mph)
January
-5.1
(22.7)
6.2
(2.47)
15 6
(9 8)
WNW
February
-4.6
(23.7)
5.5
(2 20
16.4
(10.3)
WNW
March
0.5
(33.0)
6.9
(2.72)
16.8
(10.5)
WNW
April
7.8
(46.2)
7 0
(2.77)
16.6
(10.4)
WNW
May
13.8
(57.9)
8.8
(3.47)
14.5
(9.1)
S
June
19.6
(67 3)
8.2
(3.25)
12.9
(8.1)
S
July
22.2
(72 1)
8.8
(3.49)
11.6
(7.3)
S
August
21.1
(70.0)
7.7
(3.07)
11.0
(6 9)
S
September
16.4
(61.6)
9.0
(3.58)
11.6
(7 3)
S
October
10.4
(50.8)
7.0
(2 77)
12.6
(7.9)
S
November
3.9
(39.1)
6.8
(2.70)
14.2
(8 9)
S
December
-3 0
(26 5)
6.5
(2.59)
14.5
(9 1)
S
Yearly Average
8 6
(47 6)
89.1
(35.08)
14.0
(8.8)
S
65
-------
TABLE 28.
WEATHER
CONDITIONS
AFTER SPILL
(RUFFNER AND BLAIR,
1978)
Date
Precipitation
Temperature Range
(1972)
cm
(inches)
°C
(°F)
June 6
78
(0.31)
12.7-22.7
(55-73)
7
trace
trace
8.8-21.6
(48-71)
8
1.0
(0.41)
6 1-18.3
(43 65)
9
.9
(0.37)
13.8-25.0
(57-77)
10
.03
(0.01)
7.7-14.4
(46-58)
11
0.0
(0.0)
2.7-17.2
(37-63)
12
0.0
(0.0)
3.3-19.4
(38-67)
13
0.0
(0.0)
13.3-24.4
(56-76)
14
0.0
(0 0)
16.1-27.2
(61-81)
15
.2
(0.10)
17.2-28.3
(63-83)
16
1.7
(0.69)
17.2-24 4
(63-76)
17
0.0
(0.0)
13 3-24.4
(56-76)
18
0.0
(0.0)
13.3-25 0
(56-77)
19
2.0
(0.82)
16.1-21.6
(61-71)
June
totals
17.0
(6.84)
July
totals
7 9
(3.10)
-------
3
1ARSH \3
y y v \y
UNNAMED STREAM
SPILL AREA
I - IV = CORE SOIL SAMPLES
A - H = CORE SOIL SAMPLES
1-3 = GROUNDWATER SAMPLES
SPILL AREA
RENSSELAER_CO
COLUflBIA CO
1 INCH = 0.84 KM
COUNTY ROAD
ROUNDTOP POND
Figure 14. Spill area and sampling stations (Roush et at., 1974).
67
-------
TABLE 29. FORMALDEHYDE LEVELS IN SOIL SAMPLES IN PPM
(ROUSH et a_l., 1974)
— Date of Sample _
Station Sample Depth June 7, 1972 June 29, 1972 June 4, 1973
cm (in)
detritus
ND*
11,960
ND*
0-15 (0-6) core
23,000
705
(97%)**
138
(99.4)
15-30 (6-12)
core
34,000
550
(98 4%)
ND
detritus
76,000
5,130
(93.2%)
ND
0-15 (0-6)
core
29,000
165
(99.4%)
99.
2 (99.8)
15-30 (6-12)
core
ND
2,640
ND
detritus
28,000
22,900
(18.2%)
ND
0-5 (0-6)
core
ND
700
(88.3%)
179
(97.0)
15-30 (6-12)
core
ND
240
ND
detritus
46,000
5,640
(87.7%)
0
(100)
0-15 (0-6)
core
8,000
1,470
(81.6%)
80
(99 0)
15-30 (6-12)
core
54,000
2,600
(95.2%)
ND
-------
TABLE 30.
FORMALDEHYDE
(ROUSH et aJL
LEVELS IN MARSH SOIL AND WATER SAMPLES
., 1974)
IN
PPM
Station
June
Date of Sample
7, 1972 June 24, 1972 June
7,
1973
Marsh (A-H) Mean 15 49 190
Range 12-17 200-180 90-328
Ground Water 1-3 0-4 0.5-0.5 0.89
69
-------
TOLUENE SPILL, WALLSBURG, UTAH
Background of Spill
A Hatch Company driver lost control of his truck at the intersection of
highway 189 at Wallsburg Junction on June 17, 1977. The truck overturned
blocking the road and spilling its contents of toluene. Details of the spill are
listed in Table 31. A contour map of the spill area is shown in Figure 15.
Climate of Spill Area
The weather conditions of the Wallsburg, Utah area are presented in Table
32. June, the month of the spill, is typically one of the dryest months of the
year. Winds average 14.5 kmph (8.7 mph) for the south-southeast.
Geology of Spill Area
The soil in the spill area is made up of 70% cubbly sandy/clay loam, 20% rock
outcrop and 10% other soils. Rock in the area is primarily sand stone. The
average depth of the soil in the area is 51 cm before bedrock (Woodward, 1925).
Response to Spill
The spill area was sanded by the County Highway Department. The contaminated
sand was then removed from the area (Hinshaw, personal communication, 1979). The
toluene that was not released was pumped into other Hatch Company tankers.
Highway 189 was closed for over 8 hours during the clean-up.
Environmental Levels of Spilled Material
No measurements were conducted by on-site spill personnel.
Biological Damage to Area
No biological damage was reported to area
ARSENIC TRIOXIDE SPILL, ELKHORN, WISCONSIN
Background of Spill
A Milwaukee Railroad train derailed on July 30, 1977, due to an improperly
aligned switch. Two flat cars, with two trailers on each flat car were involved
in the derailment. The trailers contained a total of 360 drums of arsenic
trioxide (200 kg each). Forty-three of these drums broke open releasing their
powdered contents. The spill site was located near a cornfield in Elkhorn,
Wisconsin. Residential areas were approximately 4 km (1/4 mile) away. Details
of the spill are listed in Table 33. A contour map of the area is presented in
Figure 16.
Climate of Spill Area
The weather conditions for the Elkhorn, Wisconsin area are presented in
Table 34 July through September are the months with the heaviest precipi-
tation The winds during summer months, when the spill occurred, are moderate
70
-------
TABLE 31. BACKGROUND OF TOLUENE SPILL, WALLSBURG, UTAH
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
Toluene
Flammable Liquid
14,146 liters
Accident(Overturned truck)
June 17, 1977
1:25 p m.
Wallsburg, Utah
Wallsburg Junction
and U189
Summit County Sheriff
71
-------
<5454
,J SPILL SITE
Corral*'
Reproduced from
best available copy.
SCALE 1 24000
o
'OOO FEE!
QUADRANGLE LOCATION
CONTOUR INTERVAL 40 FEET
dotted LINES REPRESENT 20-FOOT CONTOURS
DATUM IS MEAN SEA LEVEL
mile
Figure 15. Topography of toluene spill, area, Wallsburg
Utah (U.S. Geological Survey, 1966)
72
-------
TABLE 32. WEATHER CONDITIONS, WALLSBURG, UTAH
(RUFFNER AND BLAIR, 1978)
Average Average Average
Temperature Precipitation Wind Speed
Month °C (°F) cm (inches) kmph (mph)
January
-6.5
(20.3)
4 6
(1.83)
12.3
(7.7)
SSE
February
-3.7
(25.3)
4.1
(1 64)
13.1
(8.2)
SE
March
1 1
(34.0)
3.5
(1.40)
14.7
(9.2)
SSE
April
6.8
(44.3)
2.9
(1.16)
15.2
(9.5)
SE
May
11 1
(52 1)
2.7
(1.07)
14.8
(9.3)
SE
June
15.0
(59.0)
2.3
(0.93)
14.8
(9.3)
SSE
July
19.3
(66.9)
2.1
(0.83)
15.0
(9.4)
SSE
August
18.6
(65.5)
2.7
(1.08)
15.2
(9.5)
SSE
September
14.2
(57.6)
1.8
(0.72)
14.4
(9.0)
SE
October
8 8
(47 9)
3 3
(1.31)
13.6
(8.5)
SE
November
1.5
(34 7)
3.6
(1.44)
12.4
(7.8)
SSE
December
-3.5
(25.7)
5 0
(1 98)
12.0
(7.5)
SSE
Yearly Average
6.8
(44.4)
39.0
(15.38)
13.9
(8.7)
SSE
73
-------
TABLE 33. BACKGROUND OF ARSENIC TRIOXIDE SPILL, ELKHORN, WISCONSIN
Chemical Spilled
Class of Material
Amount Spilled
How Occurred
Date
Time
Location
On-site Spill Coordinator
Arsenic Trioxide
Poison B
8,581.9 kg
Derailment
July 30, 1977
8:05 a.m.
Elkhorn, Wisconsin
Mr. F. Haseley
Wisconsin Department of
Natural Resources
74
-------
;«l /• rri
I Hi«*
TJ0 fch
f ®Armoryfli •
f C«ntral Sch . ^ ^ * " / " /i
V , <. ///
)/&
I r"
-
SH IT ~.»•"••••! 1 • . > * >H
SPILL SITE
¦M 1023
drw«n«N*d Ftfld
1 "»tf
UiOMCrrd
CONTOUR INTERVAL 10 FEET
OATUM IS MEAN SEA LEVEL
CUAO«V.^l cJCAflO*
Figure 16. Topography of arsenic trioxide spill site, Elkhorn
Wisconsin, (U.S. Department of Geological Survey,
1971) .
75
-------
TABLE 34. WEATHER CONDITIONS, ELKHORN, WISCONSIN
(RUFFNER AND BLAIR, 1978)
Average Average Average
Temperature Precipitation Wind Speed
Month °C (°F) cm (inches) kmph (mph)
January
-9
3
(15.
2)
2
5
(0.
.99)
14
5
(9.
.1)
S
February
-7
9
(17.
7)
2.
1
(0.
,85)
14.
7
(9.
.2)
NW
March
-2.
,0
(28.
3)
4.
2
(1.
.67)
15.
6
(9.
.8)
NW
April
6.
, 7
(44.
2)
6.
9
(2.
.73)
18.
,2
(11.
.4)
NW
May
13.
.3
(56.
.9)
10.
,0
(3.
.95)
16.
,9
(10.
.6)
S
June
19.
.0
(66.
.3)
12.
.9
(5,
.11)
14.
,0
(8.
,8)
S
July
21.
.6
(71.
.0)
8
5
(3,
.36)
12.
,6
(7.
.9)
S
August
20,
.3
(68
6)
8.
,7
(3,
.46)
12.
.3
(7,
.7)
S
September
15,
.5
(60
0)
8,
.7
(3,
.46)
13.
.7
(8,
.6)
S
October
9
3
(48,
.9)
5,
. 7
(2,
.26)
15,
.8
(9,
.9)
S
November
0,
.4
(32,
,8)
4,
.6
(1
.83)
16,
.8
(10
5)
S
December
-6
.5
(20,
.2)
2,
.54
(1
00)
14,
. 7
(9
2)
S
Yearly Average
6,
.7
(44,
.2)
77
.9
(30
.67)
15.
.0
(9
.4)
S
76
-------
from the south. The weather conditions immediately after the spill are presented
in Table 35. Wind direction on the day of the spill was from the west dispersing
the compound into a cornfield. The month of August, had 12 cm (4.69 inches) of
rain or 3 1 cm (1.23 inches) over the normal amount.
Geology of Spill Area
The soil at the spill site is a Pella silt loam. The Pella series are
usually deep, poorly drained soils. The soil is a silt loam from 0-30 cm (0-12
inches), a silty clay loam from 30-107 cm (42-60 inches) and a silt loam from 107—
152 cm (42-60 inches). The estimated depth to the water table is 0-30 cm (0-1
feet). The pH ranged from 6.6-8.4 and the permeability is 1.6-6.6 cm per hour
(USDA, 1971)
Response to Spill
The derailment had damaged 43 of the 360 drums containing arsenic trioxide
releasing at most 8,582 kg (18,920 pounds) of the compound. Some of the powder
was blown into cornfields adjacent to the tracks. Railroad personnel contacted
0 & H Materials. They started clean-up of the area on July 31 and finished on
August 4. Full protective clothing, including self-contained breathing
apparatus, was used during the clean-up. Care was taken to keep dust emissions to
a minimum, however, Mr. Ehart (personal communication, 1979) noted that some
release in the wind did occur during removal of the chemical.
The broken arsenic trioxide drums were piled on the north side of the tracks
and covered with soil. On 1 August, 150 special barrels were shipped to the site
to hold the contaminated material. The contaminated soil and arsenic debris were
removed by wetting down the area, picking them up with a front end loader and
placing the material in the barrels. The contaminated materials were then taken
to an atomic waste disposal site in Sheffield, Illinois
Environmental Levels of Spilled Material
Water samples were collected from three wells and two swimming pools in the
Green Acres subdivision, ,4km (1/4 miles) south-west of the spill site. Samples
were also taken from two farm pools .8 km (1/2 miles) from the site. No arsenic
was detected in the water samples The State Laboratory of Hygiene in Madison,
Wisconsin, performed the analyses Their detection limit for arsenic was 10
PPb •
Soil samples were also collected in the area. At the spill site, before
clean-up, 7,600 ppm of arsenic were present in the soil. However, .8 km (1/2
miles) away, the levels were only 0.8 ppm (Lichtenwalner, personal communcation
1977).
Biological Damage to Area
The cornfield near the spill site was not allowed to be harvested The
arsenic was not toxic to the plants However, a bird was found dead from arsenic
poisoning 6 months after the spill, so some unnoticed biological damage could
have occurred (Ehart, personal communication, 1979)
77
-------
TABLE 35. WEATHER CONDITIONS AFTER THE SPILL
(RUFFNER AND BLAIR, 1978)
Date
Precipitation
cm (inches)
Temperature Range
°C (°F)
July 30
0.0
(0.0)
14.4-32.2
(58-90)
July 31
0.02
(0.01)
16.1-31.1
(61-88)
August
1
0.0
(0.0)
11.1-28.3
(52-83)
August
2
0.2
(0.08)
13.8-26.6
(57-80)
August
3
Trace
13.8-28.3
(57-83)
August
4
1.34
(0.53)
16.1-27.2
(61-81)
August
5
0.9
(0.39)
17.7-26.6
(64-80)
August
6
0.02
(0.01)
15.0-26.1
(59-79)
August
7
Trace
19.4-28 8
(67-84)
August
8
2.5
(0.99)
17 2-28 8
(63-84)
August
9
0.4
(0.17)
17.2-26.6
(63-80)
August
10
0.0
(0.0)
17.2-28.3
(63-83)
August
11
0.12
(0 05)
10.0-26.6
(50-80)
August
12
0.0
(0 0)
14.4-26.6
(58-80)
August
Total
11.9
(4.69)
September Total
7.5
(2.96)
78
-------
CONCLUSIONS ON LAND RESTORATION METHODS
The two acrylonitrile spills were excellent examples of innovative treat-
ments of spill damaged land. The spill response team in Leon, Kentucky, used
aeration ponds to remove the chemical from the soil. In the Dayton, Ohio, spill,
where the acrylonitrile was at or near the surface, a chemical reaction was
conducted to degrade the compound Both of these treatments were successful in
removing the acrylonitrile and were less costly, in dollars and in environmental
damage, than removing the contaminated soil.
The phenol spill in Slabtown, Maryland, also employed an interesting
treatment method. Activated carbon was used to remove the chemical from the
water leaching from the contaminated soil.
Near Kingston, Tennessee, the PCB spill could not be treated by chemical or
biological methods. Therefore, massive amounts of contaminated soil were
removed from the spill site. The data collected shortly after the spill and
several years later indicated that the PCB in the soil had not been degraded.
The previously discussed spills had all endangered surface or subsurface
waters. When the water in a spill area is not threatened, less costly treatment
methods are often used. For example the toluene spill in Wallsburg, Utah, did not
threaten waterways. The contaminated area from this spill was sanded and then
the contaminated material was removed. The nitric acid spill in Estill, South
Carolina, was neutralized with lime and contaminated soil was removed to a land
fill. In Duffee, Mississippi, the spill of sodium hydroxide was initially
treated by burying the contaminated soil. However, when residents complained
about fumes, the contaminated soil was neutralized with alum. The formaldehyde
spill in Rensselear County, New York, received no treatment. The formaldehyde
was removed from the soil by natural mechanisms within one year after the spill.
The spill of arsenic trioxide, near Elkhorn, Wisconsin, was an example of
the problems of contamination when a powder is spilled. Winds were responsible
for spreading the material and special methods were required to remove the
contaminated material from the site.
The spills discussed in greater detail in this section do not represent
a typical cross section of the treatment methods used. Mercer, et al.(1978)
reviewed the treatments applied to 78 hazardous material spills which were
reported to the Oil and Hazardous Materials Spills Branch of the EPA at Edison,
New Jersey These spills occurred from December 1975 to May 1976 A tabulation
of the treatment applied to the spills is presented in Table 36. About 11% of
the spills were chemically treated. These were acid or base spills. The acids
were neutralized with lime, limestone or soda ash. The only base spill included
in the sample, was neutralized with hydrochloric acid In 60 percent of the
spills either no treatment was applied or the treatment method used consisted
only of a water wash. Therefore, in the overwhelming majority of the spills
examined by Mercer £t a_l (1978), a quick inexpensive solution was the method of
treatment of the spill.
79
-------
TABLE 36. TREATMENT METHODS FOR HAZARDOUS MATERIAL SPILLS
(MERCER et al., 1978)
Method Used
No. of Incidents
Percent of Total
None
28
36
Water Wash
19
24
Chemical Treatment
9
11
Recovery
6
8
Landfill
2
3
Biological Treatment
1
1
Nothing Reported
13
17
Total
78
Too
80
-------
SECTION 5
FATE OF HAZARDOUS MATERIAL SPILLS ON LAND AND
POTENTIAL RESTORATION METHODS
FATE OF HAZARDOUS MATERIALS SPILLED IN THE ENVIRONMENT
Once a hazardous material is spilled on land, it can undergo a variety of
processes including:
adsorption - desorption in the soil
- leaching into surface water
leaching into ground water
chemical degradation
microbial degradation
uptake by plants and animals leading to toxic effects,
bioconcentration, bioaccumulation, and/or degradation
The goal of the spill response team is to optimize the removal of the chemical
from the environment and minimize the contamination of water supplies and toxic
effects to humans, animals, and plants. Thus, the initial response to a spill is
the removal of as much of the hazardous material from the environment as
possible. This task can be accomplished by a variety of physical-chemical
methods depending on the properties of the material spilled However,
restoration of the land requires additional efforts which can be very costly.
RESTORATION OF SPILL DAMAGED LANDS: PREVIOUSLY USED TECHNIQUES
Three techniques have been applied in the past to aid in the restoration of
spill damaged land:
remove damaged soil and replace with clean soil
wash chemical out of soil, collect and adsorb on
activated carbon
chemical neutralization
81
-------
Remove Damaged Soil
An area contaminated by a spilled chemical can be restored by removal of the
top layer of soil and replacing it with clean soil. This restoration method
utilizes only conventional farm equipment to remove the damaged soil and
appropriate clothing to protect workers from adverse effects from the spilled
chemical. The damaged soil is hauled to a secure landfill. The spill area is
then backfilled in with top soil and revegetated
Removal of damaged soil is an expensive undertaking especially if the spill
is large and significant penetration of the soil has occurred. Toxic fumes
released in the digging operation can create a serious health problem for workers
and the nearby environment. Disposal of the contaminated soil is also a major
problem since it must be hauled to a secure landfill.
Thus, removal of damaged soil is only a viable alternative if large water
supplies, a large number of people, wildlife or highly valuable land are
threatened.
Collection and Carbon Adsorption
Collection of leached water containing the spilled chemical followed by
carbon adsorption treatment to remove the chemical from the water has been proven
to be a viable spill clean-up method. This technique works best if the runoff
water from the spill area can be easily channelled into one or two carbon
adsorption units by using trenches or the land contour. If the spilled material
is efficiently adsorbed by the carbon, the effluent water can be returned to the
environment The spent carbon can be disposed of in a secure landfill or by
burning, depending on the nature of the chemical. The main disadvantages of
carbon adsorption treatment are:
continuous monitoring of the effluent is required in
order to assure that the carbon filtration system is
operating efficiently
the contour and consistency of the land may not be
suitable for collection of runoff or drainage water
without considerable excavation
long term use of carbon adsorption is expensive
Chemical Neutralization
Many hazardous chemicals can be rendered harmless by reaction with other
chemicals in a relatively simple reaction, e.g , neutralization of sulfuric acid
with base. However, unless the spilled material is near the surface and
relatively localized, neutralization procedures can cause more damage to the
land. The increased damage can be due to excess of the neutralization chemical,
heat of reaction or formation of toxic by-products. Thus, chemical neutrali-
zation must be considered on a case-by-case basis since the area covered by the
spill, the type of land and weather conditions will determine if neutralization
will prevent or cause further damage.
82
-------
Restoration of Spill-Damaged Land - New Potentially Useful Techniques
The literature was surveyed for potentially useful techniques which could
be applied to the restoration of spill damaged land. Techniques which were
identified can be divided into four categories.
microbial degradation
selective absorption by harvestable plants
revegetating the area
optimization of photochemical degradation
Microbial Degradation
In conjunction with the widespread use of pesticides on land, many
researchers have investigated the biodegradation of pesticides by microorganisms
in soil and water. A great number of microorganisms are capable of degrading
pesticides A list of some of these organisms and the pesticides they degrade is
presented in Table 37 In many instances.a pesticide that is not degraded by an
organism in a pure culture can be degraded by the organism when a supplementary
source of energy is present This phenomenon is known as co-metabolism and is an
important mechanism of pesticide degradation in the soil (Haque and Freed, 1975).
Almost all degradation transformations are accounted for by oxidative,
reductive, hydrolytic, and/or conjugative reactions; all of which are funda-
mental to all biological systems. These types of transformations and the
pesticides in which they occur and the end products of pesticide transformation
are presented in Table 38.
According to Haque and Freed (1975), there are a number of factors
influencing the rates of degradation Those factors that reduce the rate are:
sorption, unless degradation is catalyzed at
the sorptive soil surface
substitution in the ring meta to the hydroxyl of
chlorophenols rather than substitution in the
ortho or para position
The factors that increase the rate of degradation are.
presence of ester linkages separating highly polar groups
- alkaline soil
presence of clay and metallic cations
increased soil moisture
increased soil temperature
83
-------
TABLE 37. MICROORGANISMS REPORTED TO DEGRADE PESTICIDES
(HAQUE AND FREED, 1975)
Achromobacter
Aerobacter
Agrobacterium
Alcaligenes
Arthrobacter
Aspergillus
Bacillus
Botrytis
Cephaloascus
Clostridium
Corynebacterium
Erwinia
Escherichia
Flavobacter mm
Fusarium
Helminthosporium
Kurthia
Micrococcus
Micromonospora
Mucor
Mycoplana
Nocardla
Penicillium
Proteus
Psuedomonas
Rhizopus
Saccharomyces
Serratia
Sporocytophaga
2,4-D, DDT, 2,4,5-T
DDT, endrin, methoxychlor
Dalapon, DDT, picloram
Dalapon, maleic hydrazine
2,4-D, dalapon, diazinon, picloram
2,4-D, endrin picloram, tnchlorfon
Dalapon, DDT, dieldrin, heptachlor, methyl para-
thion, parathion, picloram
Picloram
PCP
DDT, lindane, paraquat
2,4-D, dalapon, DDT
DDT
DDT, lindane
2,4-D, dalapon, maleic hydrazine, picloram
Aldrin, atrazme, DDT, heptachlor, tnchlorfon
Picloram
DDT
Dalapon
Heptachlor
DDT
2,4-D, 2,4,5-T
Allyl alcohol, 2,4-D, dalapon, DDT, heptachlor,
picloram
Aldrin, dalapon, heptachlor, picloram, triclorfon
DDT
Allyl alcohol, 2,4-D, dalapon, DDT, diazinon,
dieldrin, endrin, malathion
Heptachlor
Captan, picloram
DDT
2,4-D
(continued)
84
-------
TABLE 37 (CONTINUED)
Streptococcus
Streptomyces
Tramates
Tnchoderma
DDT, heptachlor
Dalapon, diazinon
PCP
Aldrin, allyl alcohol, DDT, diazinon, dieldrin,
heptachlor, malathion, PCB, picloram
85
-------
TABLE 38. TYPES OF PESTICIDE TRANSFORMATIONS IN SOIL AND/OR PLANTS
(HAQUE AND FREED, 1975)
Type of Pesticide (or chelr
Reaction Initial Croup Reaction Product Metabolites) Involved
Oxidative
-C-H
i
-C-OH
i
Carbaryl, DDT, Dleldrln
<>¦?•
O
2,4-D, Dicamba, Hethoxychlor
2,4,5-T
-CH-CH-
-CH CH-
Aidrin, Carbaryl, 2,4-D,
Heptachlor, Plcloram
-CK-CH-
(aromatlc)
OH
I
•C«CH-
Carbaryl, 2,4-D, Dicamba,
Diuron
¦¦
V,
m'
X
9" V
c c
ci-c; ;c-
r \
2,4-D
¦¦
•"'3
-c
V0H
DDT
-C-CI
t
-C-OH
I
Dalapon, Heptachlor
¦¦
N-
l
0*
0
-------
TABLE 38. (CONTINUED)
Type of Pesticide (or their
Reaction Initial Group Reaction Product Metabolites) involved
Reductive
h0"m!
o
Parathlon
¦¦
:c-c
H H
i i
-c-c-
1 1
DDT
»
-CC1
1
-CH
i
DOT, Heptachlor, Lindane
Methoxychlor
Hydrolytlc
(addition of
water
including
oxidative
hydrolysis)
0
1 1
-c-o-f-
-c ~ HO
S0H
2,4-D esters, Malathlon
••
0
/ \
-CH CH-
OH
l
-c-c-
1 1
H OH
Dieldrin
"
0
0 ~
RO-C-N^
ROH + C02 + HN'
Carbaryl, Mexacarbate
Coojugatlve
(elimination
of water, HX
(x • halo)
and H)
-C ~ H0-
noh
-c*°
No-
2,4-D, Picloratn, Dicnnba
¦c'°
XNH-
2,4-D, Dluron, Picloram
-OH
-OCHj
2,4-D
87
-------
The above are very simple generalizations. In reality, there is interaction
between all factors and the situation is very complex. For example, compounds
that are in a highly oxidized state may resist further oxidation under aerobic
soil conditions However, the same compound may be degraded by reduction under
anaerobic conditions (Haque and Freed, 1975)
Walker and Stojanovic (1973) studied the degradation of malathion,
CH30J
P-SCHCOOC2H5
ch3° CH2COOC2H5i
an organic phosphate pesticide, on clay, loam and sandy loam under both sterile
and non-sterile conditions. As shown in Table 39, the malathion nad been almost
totally degraded in the non-sterile soil within 10 days. The degradation that
occurred in the sterile soil was attributed to chemical degradation, rather than
microbial. Microbial degradation was defined as the difference between the total
degradation and the chemical degradation. Chemical degradation appeared to be
due to alkaline hydrolysis and adsorption by the soil particles. Susceptibility
to hydrolysis increased with increasing alkalinity.
Other researchers have also studied malathion Matsumura and Boush (1968)
found that the fungus Trichodenna viride and a bacterium, Pseudomonas sp ,
degraded malathion T. viride also degraded diazinon, dichlorovos and parathion
(Matsumura and Boush, 1966)
Although malathion is rapidly degraded by soil microorganisms, malaoxon,
CH3O g
^P-SCHCOOC2H5
ch3° (!h2COOC2H5>
an oxo-analog formed either photochemically on plants or by soil microorganisms,
TABLE 39. PERCENTAGE OF CHEMICAL AND MICROBIAL DEGRADATION OF
MALATHION IN SOIL AFTER 10 DAYS (WALKER AND
STOJANOVIC. 1973)
Sample
Total
Degradation
Z Total
Chemical
Mechanisms
Degradation Due to
Microbial
Mechanisms
Clay
100
23
77
Loam
100
9
91
Sandy Loam
99
5
95
88
-------
is not degraded by microorganisms and is highly toxic (Paschal and Neville,
1976). Paschal and Neville (1976) applied both malaoxon and malathion to sterile
and non-sterile soil. The rates of disappearance of malaoxon from the soil
samples at pH of 6.2, 7.2, and 8.2 are shown in Figure 17. The data indicated that
the disappearance of malaoxon is more dependent on the pH than on the presence of
microorganisms in the soil. Thus, malaoxon disappearance is due to chemical
hydrolysis which increases with pH. Paschal and Neville (1976) also reported
that malaoxon reduced the bacterial population by 50% and the fungal population
by 95% in the non-sterile soil.
The disappearance of malathion from the sterile and non-sterile soils at a
pH of 7.2 is shown in Figure 18. Malathion was not degraded in the sterile soil.
After application of malathion, the numbers of bacteria and fungi were the same
as before the application regardless of soil pH Paschal and Neville (1976)
concluded malathion was degraded by microorganisms, while the malaoxon was
degraded by chemical mechanisms
Many researchers have studied the degradation and bioconcentration of
dalapon (CH3CCI2COOH). After treatment of plant roots with dalapon, it has been
found that the dalapon accumulates, but does not degrade in corn plants
(Blanchard e_t £l., 1960; Foy, 1961), soybean plants (Blanchard ££ £l., 1960),
cotton plants (Smith and Dyer, 1961; Foy, 1961) and wheat (Foy,1961). In none
of the above cases was pyruvic acid, one of the breakdown products of dalapon,
found in plant tissues. However, unchanged dalapon was present in plant tissues
in all cases.
Many microorganisms are capable of degrading dalapon after a lag period
during which the bacteria acclimate to the dalapon as an energy source.
Kearney e£ £^. (1964) found that species of Pseudomonas, Agrobacterium,
Bacillus, Alcallgenes, Arthrobacter and Nocardia were able to degrade dalapon in
pure cultures.
Corbin (1965) studied the effect of dalapon on soil invertebrates. He
reported dalapon applied at 22.4 kg/ha (40 lb/A) or 11.2 kg/Ha (20 lb/A) did not
affect wire worm populations. A dosage of 11.2 kg/ha (20 lb/A) resulted in
slightly increased numbers of millipedes and springtails the first year and an
increase in numbers of mites in the first and second years.
Day et al. (1963) reported the rate of degradation of dalapon was not
related to soil texture, cation-exchange capacity, total organic matter, or
source, but was related to differences in populations of soil organisms.
Kuwatsuka and Niki (1976) studied the degradation of PCP, 2,4-D, paraquat
and diquat.
89
-------
100
NOT
STERILE STERILE
pH 6.2
LL)
CJ
os
UJ
Q.
v
ry
M
z
M
<
o
X
o
c
<
£
5
4
3
2
1
TIME (DAYS)
Figure 17- Disappearance of malaoxon in sterile and non-sterile soil samples
at pH 6.2, 7-2 and 8.2 (Paschal and Neville, 1976).
90
-------
100
O NOT STERILE
• STERILE
i-
cc
«t
18
24
0
12
6
TIME (HOURS)
Figure 18. Disappearance of malathion iri sterile and non-sterile soil samples
at pH 7.2 (Paschal and Neville, 1976).
91
-------
QH OCIfeCOON
- #: - 7
CI "
(hoo]¦»)
- ([op]'"' *)
on flooded and non-flooded soil conditions. They found the degradation of
these chemicals to be affected by many factors
organic matter content
kind of clay minerals
clay content
pH
redox potential
moisture content
structure and texture of soil
The different pesticides were affected differently by each of these properties
PCP degradation was approximately proportional to organic matter content
and PCP degraded faster at higher temperatures under flooded conditions Under
non-flooded conditions, differences in soil temperatures did not make much
difference in degradation rates (Kuwatsuka and Niki, 1976) Although PCP was
degraded rapidly under flooded conditions, 2,4-D was degraded more rapidly under
non-flooded conditions (Kuwatsuka and Niki, 1976) Kuvatsuka and Niki (1976)
also found that repeated application of PCP resulted in accelerated degradation
which took place by both microbial mechanisms and non-microbla 1 mechanisms In
the microbial degradation of PCP, chlorine is liberated and metabolic products
are partly incorporated into microbes and finally metabolized to carbon dioxide
(Kuwatsuka and Niki, 1976)
Kuwatsuka and Niki (1976) also studied the degradation of dipyriaynium
herbicides, such as paraquat and diquat They found that these pesticides were
adsorbed onto soil particles ana that degradation in the soil did not take place
However, paraquat was easily degraded by Lvpomvces starkei in an aaueous culture
medlum
Chen e£ al (1977) investigated the adsorption of DDT, and dieldrin.
92
-------
DDT f
CI
A
dleldrin
f " Cl ^
ci
J
1 /
V. H H J
by potato plants under subtropical conditions. They applied DDT and dieldrin at
a rate of 5 kg of active ingredient/ha to the soil in the fall and again in the
spring. Immediately after the first application, sweet potatoes and white
potatoes were planted The persistence of the two chemicals was found to be
similar. During the fall and winter, DDT declined by only 20%, dieldrin by 25%.
However, the decline was accelerated during the spring and summer, despite the
additional spring application of the chemicals. Soil residues of DDT were lower
at the end of the summer than before the second application in the spring The
concentration of dieldrin at the end of the summer was identical to the
concentration before treatment.
These insectcies were adsorbed by the potatoes either as the parent
compounds or their metabolites (Chen et al., 1977), as shown in Table 40. The
higher the concentration of insecticide in the soil, the higher the concentration
in the plants.
From their studies,Chen £t a_l. ( 1977) determined that the time required for
50% of the p,p'-DDT to disappear in the winter was 8 months, for dieldrin 7.5
months They concluded that the rapidity with which the insecticides were
degraded was due to the subtropical conditions.
Byast and Hance (1975) examined the capacity of 4 soil samples from Viet Nam
to degrade 2,4,5-T l^C-carboxyl labelled 2,4,5-T butyl ester was applied to 2
samples to give a concentration of 1 ppm; the other two samples had a
concentration of 15 ppm. The soils with 1 ppm evolved 64-69% of the ^C02 in 49
days while the soil with 15 ppm evolved 74-96% as ^C02 in 168 days. Although
Byast and Hance (1975) tried to extract the 2,4,5-T remaining in the soil, they
were able to extract only 4% of the quantity applied at 1 ppm and 1-16% of the 15
ppm application. Presumably, the mextractable 2,4,5-T had been incorporated
into the soil organic matter.
Stojanovic £t al. (1972) investigated the effects of twenty analytical
grade pesticide standards, 20 pesticides formulated with liquid carriers and 7
mixtures of these formulations on a calcareous loam soil. The extent of
biodegradation was determined from the amount of CO2 evolved and the effects on
microorganisms determined from plate counts. The pesticides applied were
Atrazine
Bromacil
Dieldrin
Diuron
2,4,5-T
Trifluralin
93
-------
TABLE 40 INSECTICIDE ADSORPTION BY SWEET POTATOES AND WHITE POTATOES
FROM TREATED SOIL (CHEN ET AL , 1977)
Season
Crop
Recovered from Crops,
ppm
p.p'
-DDT
DDT
p.p1-DDE o.p1
-DDT
Dieldrin
Fall 1974
Sweet potato3
0.15
±0.05
0.02 ±0.01 0.06
±0.03
0.07 ±0.02
White potato'5
0.26
±0.11
0.03 ±0.01 0.09
±0.07
0.33 ±0.10
Spring 1975
Sweet potatoc
0.06
±0.00
0.02 ±0.01 0.03
±0.00
1.05 ±0.16
allarvested on
April 14, 1975.
^Harvested on March 4, 1975.
cHarvested on September 15, 1975.
-------
Dalapon
Paraquat
Dicamba
Carbaryl
2,4-D
Malathion
DDT
PMA
DNBP
DSMA
Vernolate
Zineb
DBCP
Picloram
The amount of pesticide applied was 11,227 kg/ha (5 tons/acre) of active
ingredients. Soil samples were incubated for 56 days. Of the analytical
standards, those that were degraded were picloram (36% degraded), dieldrin and
paraquat (13%) and vernolate (3%). Dieldrin historically thought to be highly
residual in soil, was probably chemically decomposed into biodegradable products
which were in turn degraded by microorganisms (Stojanovic et al., 1972).
The remaining pesticides inhibited the release of CO2 from the soil samples,
1 e., the soil samples released less CO2 than the control sample which had no
pesticide added. Half of the pesticides resulted in 10 to 30% reduction of CO2
production. DNBP and 2,4-D showed the greatest inhibitory effect.
All of the analytical pesticides reduced the number of bacteria except
bromacil and DBCP which increased the number of bacteria. Picloram and DNBP
affected the bacterial count most severely. Streptomyces population were only
slightly affected by the pesticides. Only diuron, dalapon, dicamba, picloram and
DNBP reduced the number of viable Streptomyces. The soil samples treated with
the remainder of the pesticides had increased Streptomyces populations over that
observed in the control samples.
Fungi also survived the pesticides better than the bacteria. Vernolate,
2,4-D, dalapon, pichloram, zineb, bromacil, dicamba, 2,4,5-T, trifluralin and
atrazine increased the numbers of fungi. However, DSMA, malathion, carbaryl,
DDT, dieldrin, diuron, DBCP and paraquat reduced the numbers of fungi while PMA
and DNBP killed off the entire fungal population (Stojanovic e_t , 1972).
Of the pesticide formulations, about half were degraded, while the other
half inhibited the release of CO2 from the soil. According to Stojanovic
et al (1972), picloram and 2,4,5-T were degraded the most, 91% of the 2,4,5-T
carbon was given off as CO2 and 80% of picloram carbon was given off as C02-
Malathion, trifluralin, paraquat, DDT and dieldrin were also slightly biode-
graded.
Of pesticide formulations tested, only soils treated with carbaryl had
higher bacterial population than the soil samples. All other pesticides
formulations reduced the number of bacteria. Malathion, DNBP, zineb, and
picloram severely inhibited the bacteria (Stojanovic et ail., 1972) The fungi
were inhibited by 9 pesticides and 2 pesticides, PMA and DNBP, completely
eliminated the fungi from the soil.
The seven mixtures of pesticides studied by Stojanovic et al^. (1972) and the
amount of CO2 evolved from each analysis are listed below
95
-------
Mixture
Percent
1)
2,4-D and 2,4,5-T
70
2)
Malathion, trifluralin and 2.4,5-T
45
3)
Paraquat, DSMA, diuron and zineb
20-30
4)
DDT, dieldrin, and carbaryl
2f'.-30
5)
Carbaryl, vernolate, and PMA
20-30
6)
Picloram, dicamba, and dalapon
0
7)
DBCP, bromacil, DNBP, and atrazine
0
Stojanovic et £l. (1972) concluded that mixtures of pesticide formulations were
more likely to be biodegraded than single compounds if at least one of the
pesticides in the mixture was relatively easily biodegraded. Of the 7
formulation mixtures, No. 3 and No. 5 were degraded by bacteria; the others
inhibited bacterial growth.
Stojanovic et al. (1972), found that the streptomyces and fungi were more
resistant to the pesticide mixtures than the bacteria. Mixtures Nos. 1,4, and 6
inhibited growth of streptomyces However, a 5-15 fold increase in the growth of
streptomyces occured with the other mixtures. The only mixture that inhibited
fungal growth was No. A.
Although a number of researchers have found that many pesticides are
degraded by microorganisms, other researchers have stated that many pesticides
persist in the soil, some for a number of years, as shown in Table 41.
The main research emphasis on microbial degradation in soils has been aimed
at the persistant pesticides However, Tiedje (1977) has reported on the
influence of environmental parameters on EDTA biodegradation in soils. He
applied l^C-EDTA in concentrations ranging from 440 to 1000 ppm to a variety of
soils collected at various times of the year.
EDTA biodegradation occurred in all soils as shown in Table 42, although the
subsoil samples had only a minimal amount of degradation. The higher concen-
trations (500 and 100 ppm) initially were inhibitory, but eventually stimulated
biodegradation. Tiedje (1977) suggests that because of chelating action, the
1000 ppm concentration increased the availability of soil organic matter for
microbial attack.
An increase in incubation temperature of the soil and EDTA, from 10° to 30°C
resulted in an increase in rate of degradation, as evidenced by the percent
recovery of ^C02- Tiedje (1977) suggested that a thermotolerant population was
selected which catalyzed the EDTA degradation Tiedje (1977) also reported that
samples collected in the winter yielded the highest rate of degradation; those
96
-------
TABLE 41. PERSISTENCE OF PESTICIDES
IN SOIL
Name
Persistence
Reference
Aldrin
>15 yr
Lichtenstein et al. (1971)
Chlordane
>15 yr
Stewart and Chisholm (1971)
DDT
>15 yr
Stewart and Chisholm (1971)
DIcamha
4 yr
Burnside et al. (1971)
Diuron
>15 months
Weldon and Timmons (1961)
2,4-D
>103 days
Burger et al. (1962)
Endrin
>14 yr
Nash and Woolson (1967)
Heptachlor
>14 yr
Nash and Woolson (1967)
Lindane
>15 yr
Lichtenstein et al. (1971)
Parathion
>16 yr
Stewart et al. (1971)
PCP
>5 yr
Hetrlck (1952)
2,4,5-T
>190 days
DeRose and Newman (1947)
Toxaphene
>14 yr
Nash and Woolson (1967)
-------
TABLE 42 BIODEGRADATION OF ^C-CARBOXYL EDTA ( 4 PPM) IN A VARIETY OF SOILS (TIEDJE, 1977)
Sample pH Rate of EDTA Total ^C02
Source Soil Use (H ;0) degradation 15 weeks 45 weeks
§ 4 weeks
Michigan*
Houghton muck
Vegetables
5.9
2.6
10.5
—
Houghton muck subsoil
-
6.1
0 8
3.5
Miami sandy loam (si)
Pasture
6.0
10 0
44.5
Brookston loam (1)
Forest
6.8
11.0
43.5
Conover (si)
Soybeans
6 7
12 2
46.0
Spinks loamy fine sand(lfs)
Corn
6 4
11.3
32.0
Spinks Ifs subsoil
-
6.3
0.6
3.5
Spinks (si)
Forest
4.6
-
19.0
Conove> (si)
Corn
7.4
6. 7
27.5
Conover (si) subsoil
-
7.6
0.8
4.0
F lorida
Roc led a 1 e
Tropical Fruits
7.9
9.0
34.0
Idaho
Portneuf sicl
Sugar Beets
7.9
1.8
9.5
Callfornia
Yolo I
Cereals beans
7 6
3.0
13.0
Kansas
Maron I
Sorghum
5.9
1.9 (4 2)§
13.0
+Rate calculated from best linear fit of plotted values in the 5-8 week incubation period.
+Samples collected in February.
§Accelerated rate of degradation which began at 10 weeks of incubation.
-------
collected in the summer had the lowest. He suggested that the organic material
that became available for microbial attack due to periods of freezing and thawing
accounted for the increase in degradation in the winter-collected samples.
From the data found in the literature review, it appears that microbial
degradation is a viable method for removal of hazardous materials, especially if
conditions are optimized in favor of biodegradation. Three techniques for
biodegradation of spilled hazardous materials are possible:
optimization of conditions for degradation by existing
soil organisms
application of a variety of organisms, e.g.
sewage effluent
application of microorganisms known to
metabolize the spilled material.
Optimization of conditions for degradation by existing soil microorganisms can
take the form of addition of water, nutrients, changing pH or providing
additional aeration by plowing. All of these factors have been shown to affect
the ability of soil microorganisms to degrade hazardous chemicals.
If the natural surviving soil microorganisms are killed, suitable organisms
can be provided in order to bring about degradation of the chemical. These
organisms can be applied as mixed cultures, adapted mixed cultures or as a single
culture known to be capable of degrading the chemical. However, additional
research is necessary in order to provide a methodology that will be applicable
on a wide scale.
Uptake and Effects of Chemicals on Plants
Organic Chemicals—
The effect of various herbicides, fungicides and related chemicals on plant
activity has been investigated in various studies. The objective of these
studies was to achieve a better understanding of the ecological impact of these
substances in the environment. Zutshi and Kaul (1975) studied the cytogenetic
activity of several fungicides in barley (Hordeum vulgare and Vicia faba).
Barley seeds were soaked in each test solution, washed and planted in glass Petri
dishes Seedling injury was calculated by the height attained by the first leaf.
The results of various fungicide treatments on seed germination, seedling injury
and genetic aberrations in barley are listed in Table 43 These data indicate
that Copperson Bernlate, Lonocol, Dexon, Ceresan, Hexason and Karathane are the
most injurious to seedlings The secondary roots of Vicia faba were exposed
to the more toxic fungicides. The results of these treatments are presented in
Table 44 Of the fungicides tested, Dexon caused the greatest number of cellular
aberrations.
The use of herbicides such as 2,4-D (2,4-dichlorophenoxyacetic acid) in
orchards is common practice. However, this herbicide can damage trees if
sprinkler irrigation follows soon after 2,4-D application. Larsen (1974)
reported injury to 8 year old pear trees due to 2,4-D application to a grass cover
99
-------
TABLE A3. EFFECTS OF VARIOUS FUNGICIDE TREATMENTS ON SEED GERMINATION, SEEDLING INJURY AND
CHROMOSOME ABERRATIONS IN BARLEY (ZUTSHI AND KAUL, 1975)
Fungicides Germination Seeding Chromosome Aberrations/ce11 % Abnormal
. % of Control % Tnyirv Bridflps Fragments Cells
Control
100.00
-
-
-
1
Copper Compounds
-
-
-
-
-
Coppersan (45.5)
64.30
52.23
0.08
0.13
13
Copper Dust
93.00
8.45
0.00
0.01
1
Copper Blue
96.66
6.21
0.00
0.01
1
Carbamates
-
-
-
-
-
Benlate
78.56
46.76
0.04
0.75
41
Lonocol
81.90
34.57
0.02
0.27
27
Fermale
73.46
19.89
0.01
0.05
5
Cuman
86.33
22.38
0.01
0.03
4
Di thane (M^)
92.00
12.43
0.00
0.03
3
Dithane (Nebam)
95.66
10.94
0.00
0.02
-
Sulphur Compound
-
-
-
-
-
Dexon
73.56
53.23
0.04
0.063
45
Mercury Compounds
-
_
_
_
(continued)
-------
TABLE 43 (continued)
Fungicides
Germination
% of Control
Seeding
% of Inlury
Chromosome Abberations/Cell
Bridges Fragments
% Abnormal Cells
Hexason
73.40
24.62
0.05
0.12
15
Cerasan
73.66
42.03
0.06
0.18
16
Amide
-
-
-
-
-
Orthocide +
(60)
93.66
11.93
0.01
0.07
5
Orthocide +
(75)
90.70
9.94
0.01
0.04
3
(Captan)
-
-
-
-
-
Carbonate
-
-
-
-
-
Morestan
90.33
22.37
0.05
0.11
11
Crotonate
-
-
-
-
-
Karathane
27.45
50.74
0.11
0.36
22
-------
TABLE 44 THE TYPES AND FREQUENCY OF CHROMOSOMAL ABERRATIONS PRODUCED BY 30 MIN TREAT-
MENT WITH VARIOUS FUNGICIDES IN THE SECONDARY ROOTS OF VICIA FABA (ZUTSHI AND
KAUL, 1975)
Recovery Abberration/100 Cells:
Interval Chromatid Isolocus Chromotld Various Abberrations
Treatment In Hours Breaks Breaks Exchanges Others Per Cell
1 Lonocol
(0.025%)
2 Benlate
(0.025%)
3 Dexon
(0.025%)
4 Cerasan
(0.025%)
5 Hexason
(0.025%)
6 Morestan
(0.025%)
7 Coppersan
(0.025%)
8 Karathane
(0.025%)
24
48
24
48
24
48
24
48
24
48
24
48
24
48
24
48
6
3
9
18
6
9
6
8
3
1
1
0
4
6
2
4
14
26
28
60
53
56
14
26
14
20
10
14
20
14
6
9
0
3
0
9
16
9
14
18
6
8
0
14
11
10
6
9
12
19
6
16
30
26
14
12
2
6
8
4
11
14
12
13
0.32
0.51
0.43
1.06
1.05
1.00
0.48
0.64
0.25
0.35
0.19
0.32
0.46
0.44
0.26
0.35
-------
crop adjacent to a pear tree row followed by sprinkler irrigation within 24
hours. Fall leaf abscission was inhibited and foliage development was abnormal
the following spring.
The effect of crude oil on the growth of corn (Zea mays L) was investigated
by Udo and Fayemi (1975). Germination and yields were drastically reduced as
levels of crude oil increased (see Figure 19). At 4.2% crude oil by weight of
soil, the average reductions were 50% and 92% in germination and yield,
respectively. Poor growth was attributed to.
suffocation of the plants
interference with plant-soil-water relationships
toxicity from sulfides and excess magnesium during growth
decomposition of the hydrocarbons
Metals—
Vegetation is an intermediate reservoir through which trace metals move to
other living organisms. The quantities and forms of trace metals that enter,
are distributed within the plant reservoir, and eventually migrate to other
locations in the ecosystem, are of basic importance. Metals may be localized in
roots and stem, or they may accumulate in non-toxic form. In some plants
potentially toxic metals are bound at the cell walls of roots and leaves thereby
protecting sensitive intracellular areas. A diagram of trace-metal cycling in a
plant-environment system is presented in Figure 20.
Berry (1977) studied the effects of acute toxic levels of copper and zinc on
germination and growth in lettuce seeds. Dose response curves were plotted of
root length vs. heavy metal concentration. These curves are shown in Figure 21.
Root length was reduced 50% by heavy-metal concentrations of 115 microequiva-
lents/liter for zinc and 16.5 microequivalents for copper. Acute toxicity in
lettuce (the concentration at which these metals become toxic to seedling
development) was 66 microequivalents/liter for zinc and 15.7 microequiva-
lents/liter for copper.
The ability of bush-bean plant roots (Phaseolus vulgaris L ) to act as a
barrier to translocation of certain metals was investigated by Wallace and Romney
(1977). The plants were grown in a greenhouse in 3700 ml nutrient solution for
12-21 days They were then transplanted to solutions containing various
concentrations of heavy metals. Reasonably uniform distribution between roots
and shoots occurred for zinc, manganese, nickel, lithium and boron. Iron, copper,
aluminum, cadmium, cobalt, and molybdenum were usually distributed in roots but
some large quantities occurred in shoots. Lead, tin, titanium, silver, chromium,
vanadium, zirconium and gallium were found primarily in the roots Specific
distribution of some trace metals among Phaseolus vulgaris L plant parts are
listed in Table 45
The influence of diammonium phosphate and pH on the uptake of heavy metals
(chromium, copper, nickel, lead and zinc) by corn (Zea Mays L.) was studied by
103
-------
100
UJ
o
20 -
5 6 7 8
9 10 11
3 4
1 2
POLLUTION LEVEL - X OIL IN SOIL
Figure 19. Effect of the level of crude oil addition to the soil on the
germination of maize grains (Udo and Fayemi, 1975).
104
-------
FALLOUT SHEDDING
LhALHINti
GUTTATION
—» WASHOUT
DIFFUSION
lINTERCEPTIONI
[LOS
LEAF
FRUIT
STEM
—>
COTYLEDON
TRANSLOCATION
RETENTION
IPTAKE
ROOT
EFFLUX
REDOX
SUPPORTING MEDIUM
Figure 20. Diagram of trace-metal cycling in a plant-environment system
(Tiffin, 1977).
105
-------
E
u
V
3C
J—
o
z
IU
_l
COPPER
ZINC
0.2
1000
200
400
100
A 10 20
METAL CONCENTRATION, MICROEQUIVALENTS/LITER
40
Figure 21. Dose-response curves of seedling lettuce subjected to acute zinc and copper
toxicity (Berry, 1977).
-------
TABLE 45. TYPICAL DISTRIBUTION AMONG PLANT PARTS OF PHASEOLUS VULGARIS L. OF SOME TRACE METALS
(DRY-WEIGHT BASIS) (WALLACE AND ROHNEY, 1977)
Plant Part
Aluminum
Nickel
Cobalt
Lead
Iron Copper
Manganese
Zinc Molybdenum
With Regular Solution Culture
Roots
70
2
3.5
12
3900 44
185
124 35
S terns
4
6
0.3
5
74 7
16
42 21
Leaves
10
6
0.4
0
Lower Leaves
335 17
116
85 16
Upper Leaves
213 11
54
46 9
With Elevated Levels
in Solution
Cultures
Roots
276
400
300
200
Stems
6
400
178
15
Leaves
16
400
139
9
With Elevated Supply
of Specific
Trace Metals
Roots
5000 269
711
350
Stems
110 69
460
324
Lower Leaves
710 95
772
303
Upper Leaves
358 86
605
244
2% Vegetative Yield
Depression for Elevated Supply
Whole Plant
9
99
57
13
50 71
52
29
-------
Mortvedt and Giordano (1977). Their results are presented in Table 46. In
general, heavy metal uptake is favored by acidic soil. The presence of
diammonium phosphate also tends to increase plant uptake of heavy metals.
Vegetables grown in Sango silt loam (pH 6.4) amended with anaerobically
digested sludge containing trace heavy metals were studied for metal uptake by
Giordano and Mays (1977). Sludge from Decatur and Tuscumbia, Alabama was used.
The results of this study are presented in Table 47. Yields of most vegetables
were unaffected by applied sludge. Tomato and squash yields increased
significantly. Zinc and cadmium tended to accumulate in radish and turnip roots.
Lettuce was the greatest accumulator of zinc, cadmium and copper among the leafy
vegetables. Beans, okra pods, tomato, pepper and squash fruits contained less
heavy metal than did the vegetative tissue.
The data gathered in the literature survey indicates that uptake of
chemicals, especially metals, does occur in plants. This uptake can be aided by
controlling soil pH and phosphate content. Thus, the use of harvestable
vegetation to concentrate metals from the soil appears to be a viable technique
for restoration of land damaged by spills of heavy metals. Sufficient
information is not available to assess the utility of plants for uptake and
degradation of organic chemicals.
Revegetation—
The information available on revegetation of spill damaged areas is sparse.
However, insight into the problems associated with revegetation of toxic soil can
be obtained from experiences associated with restoration of strip mining lands.
Many problems are created by surface mining for coal. The aesthetic beauty
of the area is destroyed after coal stripping. Changes in the physical and
chemical properties of disturbed soil often create a hostile environment for seed
germination and vegetative growth. Barren areas are subject to sheet erosion
which contributes sediment and pollution to surrounding streams.
Revegetation of denuded areas has been a constant problem since the
beginning of surface mining. Spoil material is often too toxic for plant life to
exist Methods are being investigated for alleviation of the toxic condition so
that vegetation can establish and survive on strip mine waste lands Techniques
are also being devised to revegetate steep outer slopes with grades up to 65%.
In some localities, excellent reclamation work has been done on mined spoils
while other areas have been totally neglected. New surface grading techniques
required by some states have been introduced with partial success in sedimen-
tation and erosion control. Success or failure is determined by the management
received after grading. Fertilization and the planting of trees, shrubs, grasses
and legumes on many sites has been hindered by low pH, lack of available plant
nutrients, improper selection of adapted varieties, and climatic factors
(Bennett e£ aK, 1976) During grading, the soil surface should be left rough,
preferably with small furrows crossing the surface horizontal to the angle of the
grade This allows seed and fertilizer to be caught in the furrows and rough
surface areas which increases germination and seedling development while
decreasing soil and fertilizer losses from erosion
108
-------
TABLE 46. FORAGE YIELDS AND UPTAKE OF PHOSPHORUS AND HEAVY METALS BY CORN AS AFFECTED BY SOIL
pH AND INCLUSION OF HEAVY METALS IN REAGENT-GRADE DIAMMONIUM PHOSPHATE (CROP 1.)
(MORTVEDT AND GIORDANO, 1977)
Phosphorus
applled,
mg/pot
Heavy Metals
in diammomum
phosphate,*
PPm
Forage
yield,
g/pot
Plant
uptake of
phosphorus
mg/pot
Plant uptake, g/pot
Zinc Copper Cadmium Chromium Nickel Lead
0
200
600
200
600
200
600
200
600
0
200
600
200
600
200
600
200
600
0
0
0
200
700
2,000
2,000
10,000
10,000
0
0
0
200
200
2,000
2,000
10,000
10,000
7
42
49
48
51
46
49
45
45
6
42
53
42
49
37
54
35
49
8
64
190
73
200
68
127
63
147
Acid Soli, pH 5.7
710
910
1003
1008
1023
988
1142
1661
1799
56
116
128
140
135
147
292
311
404
Limed Soil, pH 7.6
5
51
145
56
99
54
121
44
75
128
399
350
379
277
391
512
495
564
37
155
178
167
182
186
361
221
369
7
6
8
15
31
63
173
390
726
2
7
10
13
17
55
103
181
390
5
24
25
23
24
27
28
29
28
22
23
25
23
31
23
21
20
26
7
48
53
63
51
46
43
92
119
10
30
35
32
12
25
23
32
33
18
54
54
64
58
52
65
47
48
12
37
39
38
44
30
46
44
30
*Zinc, copper, cadmium, chromium, nickel, and lead added as chlorides to diammonlum phosphate at the
given rate.
-------
TABLE 47. TOTAL YIELD AND CONCENTRATIONS OF HEAVY METALS IN VEGETABLES, AS AFFECTED BY SLUDGE
TREATMENT, 1974 (CIORDANO AND MAYS, 1977)
bpecies
and Sludge
Treatment
Yield
kg/plot
Fruit
or root concentration,
ppm
Leaf
concentration,
ppm
Zn
Cu
Cd
Ni
Zn
Cu
Cd
Ni
Beans
None
7
21
7.9
0.04
1.3
40
6.0
0.46
2.6
Decatur
7
31
7.6
0.23
2.7
179
7.8
1.70
3.5
Tuscumbia
6
28
7.4
0.07
1.8
95
5.8
0.55
2.4
Okra
None
12
40
9.2
0.13
0.7
41
6.9
0.59
1.9
Decatur
11
61
9.0
0.60
0.7
94
10.0
2.00
2.8
Tuscumbia
11
43
8.3
0.16
0.7
55
7.1
0.59
1.8
Peppers
0.71
None
23
23
10.4
0.09
1.0
68
19.0
1.7
Decatur
25
41
13.4
0.40
2.3
143
21.0
2.70
2.7
Tuscumbia
20
31
10.5
0.14
1.6
92
18.0
0.76
2.1
Tomatoes
None
23
15
3.4
0.12
1.8
49
19.0
0.66
1.5
Decatur
29
24
3.8
0.39
3.3
77
22.0
2.10
2.3
Tuscumbia
30
20
2.9
0.20
0.7
55
18.0
0.75
1.6
Squash
0.34
None
A3
47
12.8
0.03
0.9
93
14.0
1.7
Decatur
67
83
15.3
0.20
2.6
233
19.0
0.63
4.0
Tuscumbia
73
93
12.8
0.15
1.6
226
15.0
0.36
2.2
Turnips
0.59
None
13
39
5.5
0.42
1.8
52
6.3
2.9
Decatur
14
133
8.9
1.30
2.8
194
9.4
2.60
4.0
Tuscumbia
13
73
6.5
0.42
2.1
96
7.3
0.59
2.9
(continued )
-------
TABLE 47.
(CONTINUED)
Species
and Sludge Yield Fruit or root concentration, ppm Leaf concentration, ppm
Treatment kg/plot Zn Cu Cd N1 Zn Cu Cd Ni
Radishes
None - 48 3.2 0.29 3.0 56 5.5 0.92 3.9
Decatur 149 3.8 0.92 3.7 275 7.5 3.10 6.0
Tuscumbia 121 3.3 0.33 2.6 271 3.8 0.88 5.1
Kale
None 11 33 6.0 0.63 1.8
Decatur 11 161 8.1 2.30 3.5
Tuscumbia 13 113 7.6 0.63 2.4
Lettuce
None 71 12.9 1.00 2.2
Decatur 212 22.8 8.60 3.8
Tuscumbia 336 21.0 3.00 3.9
Spinach
None 168 9.1 1.00 2.3
Decatur
163 12.7 2.80 2.9
Tuscumbia 225 10.0 0.84 2.1
-------
Various forms of limestone have been used to neutralize acid spoils with
great success. The selection of the form of limestone to be used in neutralizing
acidic strip mine spoils is based upon the chemical analyses of the spoil
material to be amended. Dolomite limestone may be selected in areas lacking
magnesium, an element essential to plant life. On acid mine spoils, dolomite has
been reported almost as effective as calcite limestone in raising the pH.
Phosphate rock is a good spoil amendment for plant growth under toxic pH
conditions (pH 3.5-4.5). Phos_phate rock contains approximately 30% total
phosphorus with 4 percent available in its natural state. (It also contains 58%
calcium oxide and 0.5% magnesium). The acidic spoil will react with the
phosphate rock to release some of the components necessary to support vegetation.
An attempt is being made to use waste materials that are creating
environmental problems as soil amendments for acid mine spoils. Digested sewage
sludge, composted sewage sludge, composted garbage and fly ash are currently
being evaluated.
Supplementary nitrogen must be added if vegetation is to be established on
spoils with low nitrogen content. Chemical analyses of the spoil material will
indicate when elemental deficiencies exist.
Mulching materials are needed to alter the surface microclimate and to help
conserve moisture during seedling establishment. Various organic materials have
been studied and found to be effective as mulches- pulp, fiber, straw, sawdust,
wood chips, cured hay, chemical binding agents and in site mulches. Pulp fiber
applied by hydroseeder at the rate of 280-448 kg/ha (500-800 lb/acre) has been
moderately effective (Armeger et al., 1976), but the cost is limiting. Straw has
been an effective mulch for new seedlings on bare and untilled surfaces. When two
to three tons per acre of straw were distributed over the soil surface after
seeding, excellent seed germination resulted. Well-weathered sawdust material,
that had been leached for a minimum of a year, proved to be a very good mulching
material. Fresh sawdust had a tendency to float or move during heavy rains.
Sawdust is limited by its availability in the reclamation areas Wood chips were
satisfactory in aiding seed germination but were not as good as straw mulch for
establishing Kentucky 31 tall fescue or orchard grass. Bark and wood chips are
very bulky and mechanical equipment for application is limited. Cured hay has
been used with considerable success. Some hay may contain sufficient grass seed
to serve both as a mulch and seed source Many chemicals have been developed to
provide erosion control and soil stabilization for seedling establishment. Data
on suitability, availability, and cost of these binders are limited. When used
alone, many of these chemicals do not fulfill all purposes of a mulch. Used in
conjunction with organic mulches, some chemical binders have improved the
stability of the mulch. An economical mulch can be produced by seeding cereal
grains or summer annuals as the first crop. Wheat, barley or rye can then be
established without mulch in the fall and killed in the spring before maturity
while summer annuals are killed by frost in the fall (Armeger e_t al_., 1976).
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Many studies have been conducted to determine the suitability of various
grass species for revegetation of surface mine spoil areas in the eastern United
States (Bennett et £l., 1976). A major problem in the east concerns acidic spoils
and high levels of aluminum and magnesium. Species selection is important for
adaptation in these areas. Grass species that have shown potential for
revegetation in the eastern U.S. include tall fescue, bermuda grass varieties,
weeping lovegrass, switch grass, red top, dear tongue, bent grasses, big and
little blue stem and commercial varieties of orchard grass, bromegrass,
eyegrass and timothy (Bennett et £l. , 1976). Weeping lovegrass and bermuda grass
seem to be most adaptable to low pH mine spoils.
The use of legume species on mine spoil areas is very important. They
provide a high quality hay, rich in nitrogen and protein, while having a
beneficial influence on desirable soil microorganisms that are important in soil
transformation. Important legume species that have been studied on acidic strip
mine areas in Appalachia include alfalfa (Medicago sativa), white clover
(Trifolium repens), crimson clover (Trifolium incannatum), birdsfoot trefoil
(Lotus corniculatus 1.), lespedeza (Lespedeza sericea), crownvetch (Coronilla
varia), hairy vetch (Vicia villosa), and red clover (Trifolium pratense L.)
(Bennett £t al_. , 1976).
Revegetation alone does not tend to remove hazardous chemicals from spill
damaged land. However, revegetation along with the addition of nutrients and pH
adjustment can aid in land restoration by control of erosion, absorption of the
toxic chemical, and aiding in the growth of microorganisms capable of degrading
the spilled material. Factors which influence the success of revegetation
efforts include:
type of soil and nutrients available
climatic conditions
soil flora and fauna
selection of plant species
planting methodology
plant maintenance
These factors are interactive rendering each revegetation project a unique
situation. However, revegetation can be very successful if guidelines are
established and followed.
Before revegetation efforts are initiated, some preliminary information is
needed. This information includes descriptions of the soil and climate. The
soil should be characterized according to its physical (texture, structure,
porosity, color, water retention and aeration), chemical (toxicity, pH, salin-
ity, cation exchange capacity and available nutrients) and biological properties
(population of bacteria, actinomycetes, fungi, algae, protozoa, worms, insects,
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etc.). Climatic conditions which require characterization include temperature,
precipitation and wind speed, the soil and the climatic conditions must be
matched with the plant species. Care in matching these factors will allow
selection of plant species which possess the optimum probability of revegetating
the area. However, even with the proper choice of plants, the success of the
project depends to a large extent on the planting methodology and continued
maintenance of the area.
The next step in the process is the selection of the planting technique.
Either seeds or young plants can be used. Both techniques have their pros and
cons. Seeds are more readily available, less expensive and require less plant
maintenance because plants are naturally conditioned. However, seeds require
one to two weeks before germination. This time delay can result in significant
soil erosion and dust losses. Germination and survival of the young seedlings is
often a problem. Plant patterns are also important. Care must be exercised in
order to assure that the plants are properly spaced so that they receive adequate
sunlight, have sufficient growing area and are close enough for fertilization and
reproduction to occur. Often it is profitable to seed the area with a fast
growing grass cover followed by the more permanent vegetation properly spaced.
Maintenance of the area is necessary to insure survival and proper plant
growth. Maintenance procedures include application of nutrients to the soil, pH
adjustment to combat the continuous deleterious effects of the toxic spill,
plowing for soil aeration and watering.
Photochemical and Chemical Degradation—
Photodegradation using solar irradiation is often an overlooked method for
detoxifying such compounds as polyhalogenated organics This method is
particularly applicable in clay soils when little soil penetration has occurred
and before rains spread the chemical and wash it into the soil. Thus, to be
useful, the photodegradation technique requires immediate response.
Photodegradation of polyhalogenated organics requires two things - sunlight
and the presence of a hydrogen donor species The hydrogen donor species can be
a light hydrocarbon oil. Olive oil was recommended as the hydrogen donor species
to help photodegrade the tetrachloro-dibenzo-p-dioxin spilled in Italy in 1976
(Crosby, 1977). Laboratory studies showed that this dioxin could be rapidly
dechlorinated by sunlight if the conditions were optimized. The mechanism is a
step-wise dechlorination initiated by the absorption of light from the sun. The
resulting dechlorinated compound is relatively non-toxic and can be biodegraded
by microorganisms.
Sahai and Chauhan (1977) discussed several classes of pesticides which
could be photodegraded. The primary degradation reaction that occurred was the
replacement of a halogen group on an aromatic ring by a hydroxyl group Hautala
(1978) examined the degree of photolysis of three pesticides, 2,4-D, Parathion
and Sevm. He found that the photo decomposition of 2,4-D was a slow process
Sevin degradation was catalyzed by the presence of detergents in the soil and
this pesticide could be rapidly degraded to 1-naphthol. The photodegradation of
parathion was found to be inconsistent and could not be correlated to soil type,
soil moisture or detergents.
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Chemical degradation of hazardous materials can include oxidation, reduc-
tion, hydrolysis, isomerization, and polymerization. The major soil char-
acteristics which effect chemical degradation are pH, redox potential, surface
acidity and the availability of catalytic sites. Adsorption catalyzed hydrolysis
is the major mechanism for the degradation of diazino and some s-tnazine
herbicides (Leonard et al., 1976). Darnell (1978) examined the use of
bromination to reclaim hazardous metals and breakdown persistent organic
compounds. Bromine and water, at 300°C, can oxidize a variety of metal compounds
and orgamcs. A useable by-product of this reaction is hydrogen.
Huibregtse al. (1978) developed a system to treat land spills by
injecting grout into the soil around the spill site to isolate the hazardous
material. Then detoxification of the hazardous material can be accomplished by
oxidation/reduction, neutralization, precipitation or polymerization. Tests
were conducted on sand and clay soils contaminated with copper sulfate or sodium
hypochlorite. The grout was injected around the contaminated soil. The
¦contaminated soils were then treated to precipitate copper or to oxidize the
sodium hypochlorite. In these tests, 70-99 percent of the copper was removed and
58-100 percent of the sodium hypochlorite was oxidized.
Chemical and photochemical degradation can be useful in restoration of
spill damaged land However, criteria must be established for the applicability
of these techniques to spill clean-up and land restoration. These criteria can
then be used by the on-site spill response coordinator to decide if a chemical or
photochemical technique is applicable to a specific spill situation.
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SECTION 6
SELECTION OF CHEMICALS FOR EVALUATION OF
LAND RESTORATION TECHNIQUES
Six organic chemicals and two heavy metal salts were selected for evaluation
by the four accelerated restoration techniques. Criteria for selection of the
organic chemicals included physical form, function of group, persistence,
volatility, water solubility, potential biodegradability, and the annual amount
produced and transported in the United States. The organic chemicals selected
represented a cross-section of the 271 hazardous chemicals listed in the Federal
Register (1978) and a variety of chemical classes. The selection of a wide
variety of chemicals with different functional groups was deemed necessary in
order to demonstrate biological techniques for restoration of spill-damaged lands
which would have broad applicability in the field. In this way results from the
experiments would have a larger inference space than if only two chemicals were
tested by all the techniques. A draw back from this procedure is that the
techniques cannot be directly compared to each other. For the heavy metal salts,
water solubility and toxicity were the primary consideration for selection.
The chemicals selected for the simulated spills and the spill restoration
methods evaluated are presented below:
Technique Chemical
I Enhancement cr iMcrobial degradation chlorobenzene
by indigenous organisms Ethion
II. Addition of mixed microorganisms from formaldehyde
primary sewage effluent aniline
III. Addition of selected microbial dinitrophenol
cultures chlordane
IV. Selective absorption by harvestable lead nitrate
plants cadmium nitrate
For Technique I, chlorobenzene and Ethion were chosen for several reasons.
Monochlorobenzene is one of several compounds on EPA's hazardous materials list
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that has limited water solubility,a high vapor pressure, low soil adsorption and
is biodegradable. The U.S. production capacity for monochlorobenzene is 318
million kilograms (700 million pounds) per year (SRI, 1979). Monochlorobenzene
is listed in the Coast Guard's CHRIS list of hazardous chemical data and as a
hazardous material by the EPA (Federal Register, 1978). Monochlorobenzene is
designated as a category B substance by EPA, i.e., any discharge or spill
greater than 45.4 kg is harmful to the environment. Ethion is an organophos-
phorus insecticide produced by FMC Corporation. Ethion is a moderately persis-
tent, relatively water-insoluble compound that can be used on 37 different food
crops, cotton, sorghum and other plants. It was anticipated that these chemi-
cals would be a good test of the ability of indigenous organisms to adapt to
and degrade a spilled chemical.
Formaldehyde and aniline were evaluated in Technique II. Formaldehyde
is a high-use, high-production chemical in the U.S. The total U.S. produc-
tion capacity is 4116 million kilograms (9074 million pounds) per year (SRI,
1979). For aniline, the U.S. production is approximately 499 million kilo-
grams (1100 million pounds) per year. Preliminary tests showed that the ad-
dition of formaldehyde or aniline to soil eradicated the soil microorganisms.
If very few indigenous microorganisms are present in the soil, very little bio-
degradation will occur. Therefore, the addition of primary sewage effluent
would tend to replenish the soil bacteria population and potentially lead to
the degradation of the compound.
For Technique III, chlordane and dinitrophenol were selected. Chlordane
is a chlorinated pesticide and is persistent in the environment. Dinitrophenol
is used in the production of dyes and preserving timber. Dinitrophenol is
also a difficult compound to degrade due to its structure. Treatment of
spilled chemicals with adapted/mutant bacteria is the most involved, time-
consuming, and expensive technique studied. This technique was used on chlor-
dane and dinitrophenol because they were the most difficult chemicals to de-
grade.
In Technique IV, the absorption by harvestable plants, lead nitrate and
cadmium nitrate were selected. Lead was used because it is a prevalent and
highly used heavy metal. Cadmium was selected because of its high toxicity.
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SECTION 7
EXPERIMENTAL METHODOLOGY
ENVIRONMENTAL CHAMBER CONSTRUCTION
For the restoration of spill-damaged lands study, two 2.7 x 5.8 m
greenhouses were used. Each greenhouse contained nine enclosed environmental
chambers. The environmental chambers were constructed in groups of three with
each group supported by a wood frame. A diagram of three environmental chambers
is shown in Figure 22. The chambers were constructed of 0.6 cm extra strength
glass glued together with GE Clear Silicone Sealer. Each environmental chamber
had the following dimensions:
length - 87 cm
width - 87 cm
height - 70 cm
Each environmental chamber had a cover of 0.6 cm glass. To provide a resting
place for the cover, the inside of the tops of the chambers were framed with 2.5
cm x 2.5 cm lumber. The lumber was coated with Thompson's Water Proof Sealer to
prevent absorption of water or chemicals. The top of the frame was coated with
GE Clear Silicone Sealer to provide a cushion seal for the glass cover. An RTV
mold release compound was applied around the cover edge to prevent the glass from
sticking to the frame. This arrangement provided a cushion but not a completely
airtight seal for the environmental chamber covers.
A steady flow of fresh air through the environmental chambers was induced by
connecting the air exit line from the chamber to a vacuum system. Photographs of
the soil chambers and the air handling system are shown in Figures 23 and 24.
Fresh outside-air was admitted into each environmental chamber, recirculated
within the chambers by means of a small fan, and then passed through a water
cooled condenser, a carbon filter, a sodium hydroxide bubbler and out through the
vaccuum pump. The air system permitted all airborne chemicals to be collected
for analysis.
A liquid drainage hole was drilled in the glass bottom of each environmental
chamber. This hole was plugged with a one-hole neoprene stopper fitted with a
glass-teflon stopcock. Thus, any liquid collected in the bottom of the chambers
could be drained and analyzed.
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Coolant Water
Condenser
Carbon Filter
To
Vacuum
Pump
C02 Trap
Condenser Trap
Air
Fan |
Fan
Drains
Figure 22. Set of three environmental chambers.
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Figure 23. Environmental chambers.
Figure 24. Water cooled condenser, carbon filter
and sodium hydroxide bubbler from spill chamber.
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Two and one-half cm of sand, then 5 cm of gravel and another 2 cm of sand were
placed in the bottom of each chamber Approximately 30-45 cm of soil were then
placed in the chambers; high-organic soil in 3 chambers, sandy-loam in 3
chambers, and clay in the remaining 3 chambers. Once the chambers were filled
with soil and packed down, the soils were seeded with perennial rye grass and
allowed to equilibrate for 3 weeks.
During the application of the spill material, the operators were outfitted
with disposable lab coats, gloves, hats and booties. Each operator wore air
tight goggles and a Wilson 1200 Basic Face Piece respirator with R-21 organic
vapor filters. Once the material was applied to the soil, the chambers were
closed and the vacuum pump system put into operation. The chambers were
monitored visually every few hours Core samples were taken at 24 and 48 hours
after the spill.
Planters, 45 cm in diameter and 45 cm high, were used to study the uptake of
heavy metals by harvestable plants. A diagram of the planters and the
experimental treatments are presented in Figure 25. Twelve planters were used
for each metal. Three soils were used in the test, organic, sandy-loam and clay.
Four planters were used for each soil. For each soil, one planter acted as a
control and the other three received the heavy metal contamination.
CHEMICAL SPILLS IN ENVIRONMENTAL CHAMBERS
Before each spill, soil samples were collected to measure microbial levels,
pH, percent moisture and other chemical parameters.
Monochlorobenzene
The monochlorobenzene spill material was prepared by the addition of 1 mCi
of labelled monochlorobenzene to 18 liters of unlabelled compound. The ^C
labelled monochlorobenzene was purchased from California Bionuclear. This
compound was labelled uniformly at the ring positions. The unlabelled
monochlorobenzene was purchased from Fisher Scientific and had a purity of 99+%.
Two liters of the labelled-unlabelled monochlorobenzene mixture were spread
evenly over each chamber. A water sprinkling can was used to spread the chemical
over the soil to simulate the hazardous spill. Each environmental chamber
received 0.292 g of monochlorobenzene per square cm of soil surface, a total of
111 fj.Ci of l^C per chamber.
Ethion
The Ethion was prepared for the simulated spill in the environmental
chambers by adding 1 mCi of ^C labelled Ethion to 18 liters of technical grade
Ethion. Both the technical grade and ^C labelled Ethion were supplied by FMC
Corporation The labelling was on the backbone carbon (-S*CH2-S-).
Two liters of the Ethion were spread evenly over each chamber with a water
sprinkling can. Each environmental chamber received 0.26 g of Ethion per sq cm
of soil surface and a total of 111 fJ-Ci of ^C.
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LETTUCE
BEETS OR CHARD
BEETS/
CHARD
LETTUCE
KENTUCKY
FESCUE
GRASS
RYE
GRASS
CHAMBER A CHAMBER B
RYE GRASS
KENTUCKY FESCUE
GRASS
BEETS/
CHARD
LETTUCE
KENTUCKY
FESCUE
GRASS
RYE
GRASS
CHAMBER C CHAMBER D
CHAMBER TREATMENTS
A - CONTROL - NO METAL, pH ADJUSTED
B + D - METAL ADDED, pH ADJUSTED
C - METAL ADDED, pH ADJUSTED, CHELATING AGENT ADDED
Figure 25. Experimental design for plant uptake studies.
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Formaldehyde
The formaldehyde spill material was prepared by adding 2 tnCi of labelled
formaldehyde to 18 liters of a 37-40% aqueous formaldehyde solution. The 14C
labelled formaldehyde was purchased from Amersham. The unlabelled formaldehyde
was purchased from Textile Chemical Company
The hazardous spill was simulated by spreading two liters of formaldehyde
evenly over the soil in each chamber with a water sprinkling can. Each chamber
received 0.11 g of formaldehyde per square cm of soil surface and a total of
222 /iCi of 14C per chamber.
Aniline
Aniline, for the simulated hazardous spill was prepared by adding 1 mCi of
uniformly ring labelled aniline to 18 liters of aniline. The labelled
aniline was purchased from California Bionuclear. The unlabelled compound was
obtained from Fisher Scientific. Each environmental chamber received 0.25 g of
aniline per square cm of soil surface and a total of 111/i.Ci of per chamber.
Chlordane
Technical grade, 21% emulsifiable concentrate, was used for the chlordane
spill. Carbon-14-labelled chlordane was synthesized from 1Z,C uniformly ring
labelled hexachlorocyclopentadiene. Only 100 ^Ci of chlordane were
available, therefore, only the sandy soil received the labelled compound. Each
sandy soil chamber received 25/iCi of ^C labelled chlordane. The technical grade
chlordane was supplied by the Velsicol Company.
Two liters of a 1.1 mixture of chlordane and water were spread evenly over
each chamber using a sprinkling can. Each chamber had surface chlordane levels
of 0.2 g per square cm.
2,4-Dinitrophenol
The dinitrophenol spill was simulated by sprinkling 500 g of 2,4-dinitro-
phenol (powder) into the soil surface in each chamber to yield a surface 2,4-
dmitrophenol concentration of .07 gm per square cm.
Cadmium Nitrate
Two hundred and fifty (250) ml of an aqueous solution of cadmium nitrate
(6.8 g/1) were sprinkled on the soil surface of three of the four planters for
each soil type. This simulated spill yielded cadmium levels in the soil ranging
from 100-200 ppm.
Lead Nitrate
The simulated spill of lead nitrate was conducted in the same manner as
described for cadmium nitrate. The spill solution contained 9.2 g of lead. Lead
concentrations in the soils ranged from 100-150 ppm after the spill.
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LAND RESTORATION TECHNIQUES
Land Restoration-Technique I
The ability of indigenous microorganisms, that survive the effects of a
hazardous chemical spill, to degrade the spilled material was evaluated in Land
Restoration Technique I. The microbial population remaining after the spill was
stimulated with nutrients (treatment 1) or with nutrients coupled with aeration
of the soil (treatment 2). The chemicals used for the Technique I experiments
were monochlorobenzene and Ethion.
The restoration treatment -1 and -2 were applied to the soils 48 hours after
the spill. The initial treatments for the two chemical spills were the same. For
each of three different soil types, (each soil type was used in 3 chambers), one
chamber served as a control (untreated), another chamber received treatment-1
and a third chamber received treatment-2. The control and treatments-1 and 2
were randomly assigned to the chambers within soil types. The nutrient used in
treatment-1 was Difco Nutrient Broth (8 g/1). Two liters of the nutrient broth
were sprinkled over the soil surface to stimulate growth of the residual
microbial population. For treatment-2 the same nutrient broth was added to the
soil surface.In ddition, the top 5-7.5 cm of the soil were plowed to increase
aeration. A garden weasel was used to accomplish the plowing.
After evaluation of the results of treatments-1 and -2 in the Ethion
chambers, additional methods of treatment were evaluated. The pH of the soil had
decreased to between 4-6 after the Ethion spill. This pH value is too low for
growth of many microbes. Soil pH values were therefore increased to approxi-
mately 6-7 to optimize growth conditions for the surviving soil microorganisms.
Lime was added to the treatment-1 (T-l) and treatment-2 (T-2) chambers on days 46
and 52.
Due to the low solubility of Ethion in water, it is relatively unavailable
to microorganisms. Two methods were investigated to increase availability of
Ethion to the microbes. On day 95, Tween 80 (a surfactant, Atlas Chemical
Industries) and nutrient broth were added to the treated soil chambers. This
treatment was followed on day 120 by the application of 50% aqueous ethanol
solutions to the soils to help to solubilize the Ethion.
After day 200, small scale experiments were conducted to determine if the
hydrolysis of Ethion could be increased by the application of alcoholic sodium
hydroxide. These experiments yielded encouraging results and aqueous solutions
containing 50% ethanol and 6-8% sodium hydroxide were then applied to the T-2
environmental chambers. Three treatments of 10 liters each of ethanol/sodium
hydroxide solutions were applied to the soils from day 210-220.
Land Restoration-Technique II
For Technique II, mixed microbial cultures, obtained from primary sewage
effluent, were evaluated for their usefulness in restoring spill damaged land
Primary sewage effluent is readily available and rich in nutrients. Technique II
was evaluated on formaldehyde and aniline spills. As in Technique I, restoration
treatments were applied to the soils 48 hours after the spill. The control,
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treatinent-1 and treatment-2 were randomized within soil types. Aniline and
formaldehyde were selected for Technique II because they would reduce the
indigenous soil microbial populations to low levels. Thus, the effects from the
addition of a mixed micobial cultures could be more readily identified.
Formaldehyde Treatment—
The first treatment evaluated on the formaldehyde spill treatment-1
environmental chambers involved the addition of 3.8 liters (1 gallon) of primary
sewage effluent to the soil. Treatment-2 environmental chambers received 3.8
liters of primary sewage effluent previously cultured in solutions of 5000 ppm
formaldehyde. Thus, organisms that could survive at high formaldehyde con-
centration increased in number. It was found that the treatment—2 culture
contained primarily Pseudomonas sp. These treatments were reapplied to the
respective chambers on day 25.
Aniline Treatment—
For the aniline spill, 3.8 liters of primary sewage effluent were added to
each of the treatment-1 environmental chambers. The initial step for the
treatment-2 environmental chambers was the addition of 2 liters of a 15% solution
of hydrogen peroxide to the soil. The hydrogen peroxide was added to oxidize the
aniline to a more biodegradable form. One hour after the hydrogen peroxide was
added, 4 liters of primary sewage effluent were added to the soil.
On day 12 and day 42, small areas (900 cm2) of the T-2 chambers were treated
with 1 liter of 15% hydrogen peroxide solution. The soils were then plowed.
Also on day 42, the T-l chambers were treated with primary sewage effluent
cultured in nutrient broth containing aniline.
On day 96, the T-l chambers were treated with a mixed culture of micro-
organisms grown in a solution of aniline, nutrient broth, MgCl2, Ca(N03)2 and
KH2PO4. To provide essential minerals and nutrients for degradation, a solution
of MgCl2 (0.2 g/1), Ca(N03)2 (3 gm/1), KH2PO4 and yeast extract (1 g/1) was
applied to the T-l chambers on days 126 and 154. The T-2 chambers were treated
with the same mixture on day 170.
Land Restoration-Technique III
Technique III examined the use of mutant, adapted microbial cultures to
treat chemical spills. The two chemicals used in Technique III tests were
chlordane and 2,4-dinitrophenol. Once again the treatments were applied 48 hours
after the spill and the treatments were randomized within soil types.
Chlordane—
The microorganisms used in the chlordane spill experiment were cultured in
a mixture composed of nutrient salts, yeast extract and 21% emulsifiable concen-
trate technical grade chlordane The nutrient salts - yeast extract solutions
were made up in 4 liter quantities and had the following formulation-
6.4 g K2HPO4 1.6 g KH2PO4
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2.0 g NH4NO3
0.8 g MgSO^'l^O
0.86 g CaCl2
0.92 g FeCl.3• 6 H20
4 g yeast extract
Technical grade chlordane acted as the carbon source. The cultures were
reinoculated into fresh chlordane, nutrient salts and yeast extract solutions
every 7 to 10 days for 2 months. The reinoculation process selected the
microorganisms which could adapt to and metabolize technical grade chlordane.
Treatment-1 environmental chambers each received 4 liters of microbial culture
and nutrient salts mixture. Treatment-2 environmental chambers each received
lime, to make the soil basic, followed by the addition of 4 liters of the
microbial culture and nutrient salts mixture. The treatments with the microbial
culture and nutrient salts mixture were re-applied to the soils on days 8 and 28.
2,4-Dinitrophenol—
For the 2,4-dinitrophenol spill, microorganisms were cultured in a mixture
of nutrient salts, yeast extract and 2,4-dinitrophenol. The 2,4-dinitrophenol
was the sole carbon source. The cultures were reinoculated in the fresh media
every 7 to 10 days for 3 months. This technique selected the organisms which
could adapt to and metabolize dinitrophenol. Only six environmental chambers
were used in this spill exeriment. Three chambers were controls and three
received the microbial treatment The treatment consisted of first adding 500 g
of lime to the chambers to raise the soil pH to basic conditions. The 2-4-
dinitrophenol is water soluble under basic conditions and therefore more
available to microorganisms. Four liters of the adapted microbial culture,
nutrient salts and yeast extract were then added to the lime-treated chambers on
day 2 and day 8. No aeration of the soil was conducted.
Land Restoration Technique IV
The fourth land restoration technique evaluated the application of selec-
tive absorption of heavy metals by harvestable plants. The heavy metals used in
the Technique IV experiments were cadmium and lead. Both heavy metals were
applied to soil chambers in the form soluble nitrate salts. Four plants were
evaluated for their ability to concentrate metals in the experiment, rye grass,
Kentucky fescue grass, lettuce and either beets or chard. The experimental
design is presented in Figure 25.
To promote the uptake of the metals by the plants, two treatments were used:
The pH of the soils was adjusted to acidic values with dilute acetic acid
Chamber C (Figure 25) was treated with 400 ml of a 0.1M solution of disodium EDTA.
Plant seeds were then added to the soil chambers as shown in Figure 25. Because
the soil was made acidic
the soil was made acidic and disodium EDTA,
a chelating agent, was added to the soil
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of poor germination of the beets, Swiss chard was substituted two weeks into the
experiment. Soil pH was monitored throughout the experiment and plants were
collected from early May until mid-July.
SAMPLING METHODOLOGY
Organic Chemicals
A 30.5 cm corer with a 2 cm diameter used to obtain soil core from the
chambers. Core samples were taken according to the following schedule:
minus 2 days to establish background microbial
populations and soil parameters
spill + 24 hours
spill + 48 hours
weekly thereafter
Two core samples were taken per chamber at each sampling time. The location
of the core sites was selected from random numbers, i.e., up to 25.4 cm over
40.6 cm. The core samples were separated into 3 levels, 0-5 cm, 5-10 cm, and
10-30.5 cm. The levels from the two core samples in each chamber were pooled
for analysis, i.e.. the two samples at 0-5 cm levels were put together. Ster-
ile preweighed 250-ml polyethylene beakers with caps were used to store and
transport the samples.
The sealed beakers were returned to the laboratory, reweighed and measured
amounts of the soil were removed. One gram samples were removed and transferred
to 10 ml of sterile water for microbial analysis. Two grams were removed for
determination of soil moisture, pH, and % organic analysis, and 0.5 g for
radiozonalysis. The remainder of the sample was resealed in the beaker for GC
analysis of the chemical.
Heavy Metals
Core samples were collected with a 30.5 cm corer. Two sets of soil samples
were taken to establish heavy metal levels in the soil. The plant tissue was
collected by cutting the above ground part of the plant with grass clippers. The
plant tissue was stored in paper bags until digestion and analysis. Care was
taken in harvesting the plants to avoid surface contact of the tissue with the
metal containing soil.
ANALYTICAL PROCEDURES
The soil samples from each chamber were analyzed for the following
parame ters
soil pH
% moisture
127
-------
% organic matter
nitrate
soil bacteria
soil fungi
soil 14C activity (except dinitrophenol)
level of the spill chemical
The procedures used for each of these analyses, as well as those used to determine
the chemical content of the traps, carbon filters and the labelled CO2 content of
the NaOH bubblers are described in detail in the following sections.
Soil pH
The pH of the soil was measured by adding 10 ml of distilled water (pH 6.15)
to the soil sample and stirring for 30 minutes. The soil was allowed to settle
and the pH read using a Orion 399A meter with a 91-04 electrode standardized at
pH 4.01 and 9.18.
Percent Moisture
A weighed portion of the soil was added to a tared crucible and dried in an
oven (100-105°C) to constant weight. The crucible was then cooled in a
desiccator and reweighed. The percent moisture was calculated from the following
formula:
weight before drying - weight after drying
% moisture = 100
weight before drying
Percent Organic Matter
The weight lost by a dry soil on heating to 550° provides a general idea of
the amount of organic matter in the soil. The previously oven dried sample from
the percent moisture analysis was heated in a muffle furnace at 550°C for 30
minutes. The sample was then cooled in a desiccator and reweighed. The percent
organics was calculated by the following formula:
weight of dried sample - weight after ignition
% organics = 100
weight of dried sample
Nitrate Content
To determine nitrate content, a 2 g air dried soil sample was dispersed in
10 ml of an extracting solution containing
128
-------
16 66 g/1 AI2(304)3-18 H20
1.24 g/1 H3BO3
4.67 g/1 AgN(>3
2.43 g/1 NH2SO3H
and adjusted to pH 3 with sodium hydroxide. The sample was stirred for 20 minutes
and allowed to settle. The nitrate content was determined using Orion Research
Meter 399A with an Orion Nitrate 93-07 electrode. The meter was calibrated with
dilution of a 2000 ppm nitrate nitrogen stock solution.
Soil Microbial Populations
Each weighed sample of soil (1 g) was suspended in 10 ml of sterile distilled
water to give a 1:10 dilution. Serial dilutions were prepared from this
suspension. Dilutions of 1-100 through 1:100,000 were used, the appropriate
dilution used being determined by the microbial count of the previous week's
sample. A 0 1 ml aliquot was spread on each of 2 plates of each media for a
dilutions of 1.1000 to 1:1,000,000.
The numbers of aerobic bacteria were obtained by plating on Eugonagar
(Baltimore Biological Laboratories, Cockeysville, Md) and incubation at room
temperature for 120 hours. The average counts of the duplicate plates were
determined and corrected for one gram of soil. Yeast and mold counts were
obtained by plating dilutions on Sabouraud's Dextrose Agar (Baltimore Biological
Laboratories, Cockeysville, Md). Incubation was also at room temperature for 120
hours. The same method was used for reporting counts per gram of soil.
The activity of the soil samples was determined by an Eberline
Proportional Gas Flow Counter. Windowless operation was used with P10 gas. A
thin layer of soil was spread on a planchet and 5-one minute counts were taken.
The net count per minute (cpm) were determined by taking the average background
level plus 1.96 times the standard deviation This value was then subtracted
from the average cpm for the soil sample for net cpm. Any soil samples with net
cpm of zero or less were recorded as background levels. The soil samples were
then weighed in order to calculate the number of counts per gram.
The contents of the sodium hydroxide bubblers were removed several times
during a test to determine if any *^C02 was present. Barium hydroxide was added
to 10 ml of the sodium hydroxide bubbler solution to precipitate the trapped
carbon dioxide as barium carbonate. The precipitate was centrifuged and a sample
was dried and weighed. The 14C content of the sample was determined by an
Eberline Proportional Gas Flow Counter in the same manner as discussed above for
the soil samples.
129
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Organic Chemical Concentration in Soils, Carbon Filters and Condensers
Monochlorobezene—
Initially the procedure recommended by the EPA (Thompson, 1974) to remove
chlorinated compounds from the soils was used. In this procedure, a known
quantity of soil is placed in a Soxhlet extraction and extracted with a solvent
such as methylene chloride for 1 to several hours. A florisil column is used to
remove soil impurities and gas chromatography is used for quantitative analysis.
The results from this procedure were compared to a simplified method. In the
simplified method, 100 ml of methylene chloride were added to the weighed soil
sample in the covered plastic beaker. The soil-liquid was shaken and allowed to
stand for 1 hour. The samples were again shaken and an aliquot of liquid was
removed and filtered through a cotton plug into GC auto sampler vials. The
simplified method gave higher and more consistent results than those obtained by
Soxhlet extraction. Several reasons for the better results with the simplified
method versus Soxhlet extract are:
monochlorobenzene is not adsorbed by the soil to
any appreciable extent and is thus very easy to
extrac t
the smaller soil sample used in the Soxhlet extraction resulted
in a non-representative sample
with the smaller soil sample used in the Soxhlet, extraction,
the lower concentrations were below the GC
detection limits
some monochlorobenzene was lost during the additional
handling steps in with Soxhlet extraction
Because of the large number of samples, the simplified preparation method was
used after the second sampling.
The extracted samples were quantified using a Varian 3700 GC with
autosampler and flame ionization detector under the following conditions:
injection port temperature- 250°C
oven temperature 65°C
carrier gas: N2 at a flow rate of 30 ml/min
column: 1.5% OV-17, 1.95% OV-210 on Anakron Q 80/100
The peak areas were integrated with a Varian CDS 111. The results were compared
to a standard curve obtained with known concentrations of monochlorobenzene in
methylene chloride. Lower detection limit of the method was 1 ppm in solution.
The carbon filter and condenser contents were subjected to GC analysis by
the methodology described above.
130
-------
Ethion—
The Ethion was initially extracted from the soil samples in covered beakers
by adding 50 ml of methylene chloride, shaking the beakers and allowing them to
stand for 1 hour. The methylene chloride was then decanted and a second 50 ml of
methylene chloride was added. Both washes were then combined and put into GC
autosampler vials. However, it was determined that soil moisture and soil sample
size of 20-40 grams resulted in recovery of the Ethion from the soils. A second
procedure was then initiated to increase the percent recovery. This procedure
resulted in the recovery of approximately 90% of Ethion from the soils.
Duplicate 1-2 g samples were then taken from a soil sample and extracted in tubes
by the following procedure:
add 0.5 ml of methanol
add 4.0 ml of a 50/50 methanol/methylene
chloride solution - centrifuged and decant
add 4.0 ml of methylene chloride - centrifuge
and decant
add 7.0 ml H2O to combined organic layers
pipet bottom layer (methylene chloride)
into GC autosampler vials
The samples were quantified using a Varian 3700 GC with autosampler and
flame ionization detector under the following conditions:
injection port temperature: 290°C
oven temperature: 218-248°C
carrier gas- N2 with a flow rate of 30 ml/min
column: 1.5% OV-17, 1.95% OV-210 on Anakron Q 80/100
The peak areas were integrated with a Varian CDS 111. The results were compared
to a standard curve obtained with known concentrations of Ethion in methylene
chloride.
Formaldehyde—
The formaldehyde was extracted from the soil samples in the covered beakers
by adding 50 ml of distilled water, shaking the beakers and allowing them to stand
for 1 hour. The water was decanted from the beaker into a centrifuge tube,
centrifuged at 3200 rpm for 5 minutes. The clear liquid was then put into GC
autosampler vials. Recovery of formaldehyde from the soil was between 95 and
100%. The samples were quantified using a Varian 3700 GC with autosampler and
flame ionization detector under the following conditions:
131
-------
injection port temperature 290°C
oven temperature: 135°C
carrier gas: N2 as a flow rate of 30 ml/min
column: Porapak T 80/100 mesh
The peak areas were integrated with a Varian CDS 111. The results were compared
to a standard curve obtained with known concentrations of formaldehyde in water.
Aniline—
Duplicate 1-2 g soil samples were taken from the soil cups, weighed and then
extracted in tubes using the following procedure-
add 0.5 ml of 20% NaOH
add 4 ml of a 50-50 mixture methanol: methylene
chloride solution, centrifuge and decant solution
add h ml methylene chloride to the dirt in the tube,
centrifuge and combine decant with the methanol:
methylene chloride mixture
add 7 ml water to combined organic layers - shake,
centrifuge
pipet bottom layer into sample bottles for GC analysis
The samples were quantified using a Varian 3700 GC with autosampler and
flarae ionization detector under the following conditions:
injection port temperature: 300°C
oven temperature- programmed from 140°C to
180°C at 20°C per minute
- carrier gas* N2 with a flow rate of 30 ml/min
columns* Carbowax 20 M with 2% KOH on Chromosorb
WAW 80/100 mesh
The peak areas were integrated with a Varian CDS 111. The results were compared
to a standard curve obtained with known concentrations of aniline in methylene
chloride.
Chlordane—
Duplicate 1-2 g samples were weighed out from the soil sample and extracted
in tubes by using the following procedure-
132
-------
add 4 ml of a 50-50 mixture of methanol:methylene
chloride solution, centrifuge and decant the solution
add 4 ml of methylene chloride to the soil in the tube,
and combine with first wash
add 5 ml water to combined organic layers
pipet 1 ml of the bottom layer and put into 14 ml
of benzene, mix and load into GC autosampler vials
The samples were quantified using a Varian 3700 GC with autosampler and
flame ionization detector under the following conditions:
injection port temperature: 300°C
oven temperature.programmed from 170°C to 230°C
at a rate of 10°C per minute
carrier gas: N2 with a flow rate of 30 ml/min
column. 1 5Z OV-17, 1 95% 0V-210 on Anakron Q 80/100
The peak areas were integrated with a Varian CDS 111. The results were
compared to a standard curve obtained with known concentrations of chlordane in
methylene chloride.
Dimtrophenol—
Dinitrophenol samples were analyzed by extracting duplicate 1-2 g samples
in tubes with the following procedure:
the soil sample was air dried 30 minutes
add 0.4 ml of IN HC1
soil sample dried at 60°C for 3-6 hours
add 4 ml of a 50:50 mixture methanol/methylene
chloride, centrifuge and decant
add 4 ml of methylene chloride, centrifuge and
decant and combine with first wash
collect sample from combined organic layers for GC
analysis
133
-------
The dinitrophenol samples were quantified using a Varian 3700 GC with
autosampler and flame ionization detector under the following conditions:
injection port temperature: 275°C
oven temperature: 175°C
carrier gas: N2 with a flow rate of 30 ml/min
column: 1% SP-1240 DA 100/120 mesh supelcoport
The peak areas were integrated with a Varian CDS 111. The results were
compared to a standard curve obtained with known concentrations of dinitrophenol
in methylene chloride.
Soil and Plant Tissue Digestion and Analysis for Metals—
After collection, the soil or plant tissues were dried at 60°C for 24 hours.
The plant tissues were then weighed and ground. A 0.5-2.5 g sample was then
digested in a mixture of reagent grade nitric and perchloric acid for 2-4 hours.
After digestion, the samples were filtered through Whatman #40 filter paper and
brought up to volume with distilled water in a 25 ml volumetric flask. The
samples were then analyzed on a Varian 775 Atomic Absorption Spectrophotometer at
a wavelength of 283.3 run for lead and 228.8 nm for cadmium. The absorbance units
of the samples were compared to standards to determine the lead or cadmium
concentrations.
134
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SECTION 8
EXPERIMENTAL RESULTS
INTRODUCTION
The data from the four land restoration techniques are presented in this
section. For each organic chemical, the soil pH, soil moisture content, soil
organic content, microbial levels, and chemical levels were evaluated over time.
In addition, for five of the six organic chemicals, radiation levels were
monitored. The heavy metal vegetative uptake studies were evaluated for soil pH,
soil metal levels and plant metal levels over time.
LAND RESTORATION TECHNIQUE I - MONOCHLOROBENZENE SPILL
Soil pH
The initial pH of all the soils ranged from 5.5 to 6.5. After the mono-
chlorobenzene spill, an increase in pH of 0.5 to 1.3 units was observed. The pH
values as a function of core depth over time are presented in Table B-2, B-3 and
B-4 of Appendix B.
Soil Moisture Content
The percent moisture content of the soils as a function of depth are
presented in Tables B-5, B-6 and B-7 of Appendix B. The days when the chambers
were watered are also noted on the charts. An increase in soil moisture was
observed at all levels in all chambers after the addition of the monochloro-
benzene. This increase is due mainly to volatilization of the monochlorobenzene
during the moisture analysis procedure. The treatments were initiated after the
day 2 sampling. Both treatments-1 and 2 introduced water into the chambers.
Thus, the soil moisture content of the treated chambers is higher than that of the
controls.
Soil Organic Content
The percent organic content of the soils are presented in Tables B-8, B-9
and B-10 of Appendix B. The organic soils averaged around 16 3% organic content
in the top layer The sandy and clay soils had substantially less organic
content. These two soils had an average organic content of 5.77 and 3.22%,
respectively in the top layers. The addition of monochlorobenzene did not
increase the apparent organic content. Due to the high volatility of this
chemical, it would have been lost during the percent moisture analysis
135
-------
Microbial Population
The bacterial and fungal populations as a function of time for the organic,
sandy-loam and clay soils are shown in Figures 26-28. The middle and bottom layer
bacterial and fungal populations are presented in Figures B-l to B-6 of
Appendix B
For the organic soils, the bacterial populations generally declined after
addition of the monochlorobenzene. Fungal populations also dropped but there was
a lag period of several days before the monochlorobenzene affected the more
resistant fungi. The bacterial and fungal populations in the three layers showed
the same die-off and recovery trends.
The bacterial populations in chambers receiving treatment-1 (T—1) began
recovery within 8 days after the spill Populations at all three layers in the
T-l chamber reached their maximum levels between day 15 and 29 In contrast the
bacterial populations in the control and treatment-2 (T-2) chambers did not show
significant recovery until day 15 after which rapid growth in populations was
observed. The control and T-2 chambers paralleled each other in bacterial
recovery reaching peak populations in all soil depths on day 29.
The behaviour of the fungal populations in the three organic chambers was
more erratic than the bacterial populations. In general, a decline in the number
of fungi present in the soil was observed from day 2 to day 15. The fungal
population in all chambers began recovery between day 15 and 22. A second drop
in fungal population in the T-l and T-2 chambers was noted on day 29.
The addition of the monochlorobenzene to the sandy-loam soil inhibited the
bacterial growth in the control and T-2 surface soil samples until day 8 The T-
1 chamber had higher bacterial counts than the surface samples of the other
chambers through the 22nd day. In the middle and lower soil levels, the T-l and
T-2 chambers had relatively stable populations through the 15th day The control
chambers had higher counts than the other chambers during the first 15 days.
However, at day 22, the bacteria populations in the three chambers, at the middle
and lower levels, were similar.
The fungal counts were erratic. However, control populations for the first
15 days after the spill were higher than the T-l and T-2 chambers for all soil
depths and throughout the test for the middle and lower levels. It can also be
noted that a reduction in fungal levels occurred on the 8th day after the spill.
The fungal populations generally increased on the 22nd day.
The bacterial levels in the surface clay samples initially decrease in
numbers. On the 8th day, after the spill, the bacteria in the control chambers
had increased more rapidly than the bacteria in chambers T-l and T-2. The
bacterial populations, at the middle clay soil depths, were reduced through the
8th day for the control chambers, and the 22nd day for the T-l and T-2 chambers.
The lower layer soil bacterial levels exhibited reduction in population levels
for chambers T-l and T-2. However, the bacterial levels in the control chamber
remained relatively constant.
136
-------
60/000/000 r
10/000/000 r
<
GS
to
(X
LU
Q.
CO
fX.
UJ
CO
e
3
s
00
3
Q.
O
CL
1,000/000 -
100/000=
o CONTROL
~ TREATMENT 1
A TREATMENT 2
3ACTERIA
FUNGI
10/0CC
Figure 26. Upper Level organic soil microbial populations - monochlorobenzene
spi11.
137
-------
BACTERIA
O CONTROL
0 TREATMENT 1
A TREATMENT 2
10,000,000
<
cz
v>
1,000,000
FUNGI
o
CL
100,000
10,000
DAYS
Figure 27. Upper Level sandy soil microbial populations- monochlorobenzene
spi11.
138
-------
100,000,000
BACTERIA
10,000,000
UJ
o CONTROL
~ T-1
A T-2
c/j
0£
UJ
§ 1,000,000
C/J
FUNGI
100,000
5 0 5 10 15 20 25 30 35 40 45
DAYS
Figure 28. Upper level clay soil microbial populations - monochlorobenzene
spi 11-
139
-------
The erratic fungal populations observed in the clay soils make any
interpretation difficult. No definite toxic effects were observed on the fungi
in the clay soils.
Soil Monochlorobenzene Levels
The monochlorobenzene levels as a function of soil types and soil depths are
plotted versus time in Figures 29-31 The monochlorobenzene was essentially
removed from the organic soils after the 8th day. The sandy-loam soils
monochlorobenzene levels were low after 15 days and the clay soils mono-
chlorobenzene levels were zero after 22 days.
In the organic soil the monochlorobenzene levels in the T-l chamber were
rapidly reduced to low levels. The control and T-2 chambers retain the
monochlorobenzene somewhat longer, but after the 8th day, the monochlorobenzene
levels in the soils were similar.
The sandy-loam soil did not lose the monochlorobenzene as rapidly as the
organic soil. The control chamber had no monochlorobenzene present after the 8th
day. However, the T-2 chamber had monochlorobenzene present until the 22nd day
and in chamber T-l, monochlorobenzene was found through the 15th day in the top
two depths and the 22nd day at the lower depth.
The monochlorobenzene loss as a function of time measured for clay was
similar to the results obtained for sandy-loam soil. The monochlorobenzene was
lost from the control chamber by the 8th day. Chambers T-l and T-2 had
monochlorobenzene until the 22nd day.
Discussion
Monochlorobenzene was somewhat toxic to soil bacteria and was highly toxic
the grass. Within 1-2 hours after the spill, the grass was wilted Twenty four
hours later, it had completely turned brown. Monochlorobenzene was rapidly lost
from the soil as evidenced by the high concentration of monochlorobenzene found
in the carbon filters and traps. The loss of monochlorobenzene by evaporation
from the treated chambers was retarded due to the addition of 2 liters of nutrient
broth during treatment. The addition of liquid tended to push the mono-
chlorobenzene deeper into the soil and hold it there longer.
No evidence of microbial degradation of monochlorobenzene was observed
during the tests. No additional compounds were seen in the GC traces, and no
^C02 was found in the sodium hydroxide bubblers. However, the monochlorobenzene
soil levels correlated well to the bacterial levels. The bacterial populations
were depressed when significant monochlorobenzene concentrations were in the
soil As soon as the monochlorobenzene had evaporated from the soil, the
bacterial populations recovered.
140
-------
O CONTROL
0 TREATMENT 1
A TREATMENT 2
CD
c_
O
o
~)
in
_1 MIDDLE (5-10 cm.)
ILI
>
UJ
CD
O
CtL
O
_1
LOWER (10-30 cm.)
2
x
o
z
1
0
DAYS
Figure 29. Monochlorobenzene concentrations in the organic soils.
-------
LEVEL
UPPER (0-5 cm.)
O CONTROL
~ TREATMENT 1
A TREATMENT 2
2 _
MIDDLE (5-10 cm.)
2
0
2
LOWER (10-30 cm.)
1
0
DAYS
Figure 30. Monochlorobenzene concentrations in the sandy soils.
-------
UPPER (0-5 cm.)
3
CONTROL
TREATMENT
2
TREATMENT
1
JHl
~ ^ r -
2 MIDDLE (5-10 cjjk
1
0 h.
2 LOWER (IG-JO cm.)
1
0
DAYS
Figure 31. Monochlorobenzene concentrations in the clay soils.
-------
The simulated spill of monochlorobenzene was a good example of the movement
of a volatile, low polarity, low water solubility compound in soils. The
monochlorobenzene evaporated from the soils tested within 28 days after the
spills The treatment methods applied to the soils were relatively ineffective
because they involved wetting the soil surface. The wet soil reduced the
evaporation rate of the monochlorobenzene in the treated chambers. The control
chambers, which did not receive any water after the spill, had uninhibited
evaporation of the monochlorobenzene from the soil and recovery of normal soil
fauna.
LAND RESTORATION TECHNIQUE I - ETHION SPILL
Soil pH
The pH values of the organic, sandy-loam and clay soils as a function of soil
depth and time are compiled in Tables C-2, C-3 and C-4 of Appendix C. The initial
pH levels of the organic soils were near neutral. However, after the Ethion
spill, the soil pH values dropped to the 5-6 range. The pH levels in the control
chamber remained in the 4.7 to 5.4 region throughout the remainder of the test.
The soil in the treated chambers was limed on days 48 and 55. The lime increased
the pH to near neutral levels. However, by day 94, the pH had again decreased to
between 5 and 6 units. The treated chambers received the ethanol-NaOH treatments
after day 200. Soil pH levels after treatment ranged from 9.6-12.5.
Sandy soil pH levels were also initially near neutral. For the first nine
weeks after the Ethion spill, the soil pH values ranged from 3.3-6.0. The soil
pH in the control chambers after the spill ranged between 4.0-5.4 units for the
remainder of the study The treated chambers were limed days 48 and 55 raising
the pH values to between 6.0 and 7 3. Over the next 60 days, the sandy soil pH
values decreased by one or two pH units. The ethanol-NaOH solutions were applied
to the treated chambers after day 200 raising the pH values to between 10 0-11.4
Initial pH levels of the clay soils were 6.4. After the Ethion spill, soil
pH levels ranged from 3.7-4.5. The pH levels in the control chamber ranged from
3.2-5.9 for the remainder of the study. The treated soil chambers were limed on
days 48 and 55. The lime raised the pH of the clay soils to near 6.0 units After
day 200, ethanol and NaOH solutions were applied to the treated soil chambers
The soil pH levels were raised to levels from 10.0-10.9.
Soil Moisture Content
The percent moisture levels as a function of soil type, depth and time are
compiled in Tables C-5, C-6 and C-7 of Appendix C. The moisture content in the
upper layer of the control organic chamber ranged between 6.6-35.8% and averaged
near 18%. The T-l organic chamber had moisture levels in the upper layer of soil
ranging from 10.0-42.1% and averaged near 22%. The T-2 organic chamber had
moisture values in the upper layer of soil ranging from 12.0-36.5% and averaged
near 25%.
The moisture levels in the upper sandy soil layer in the control chamber
ranged from 7 3-38.4% with an average of 16%. The T-l sandy soil chamber had
144
-------
moisture levels in the upper soil layer ranging from 8.8-25% with an average of
20%. The T-2 chamber had percent moisture values in the upper soil layer ranging
from 5.6-32.3% with an average of 18%.
The moisture levels in the clay control chambers upper layer, ranged between
5.9-24.3% with an average of 14%. The T-l chamber had percent moisture levels in
the upper soil layer, ranging between 3 7-21.3, with an average of 12.3% The T-
2 chamber had moisture values in the upper soil layer ranging from 3.2-25.4%,
with an average of 15.4%.
Microbial Populations
The bacterial populations in the organic soil, top layer are presented in
Figure 32. Bacterial populations dropped substantially in the first two days
after the spill. The treated soil bacterial levels recovered quickly due to the
nutrients added to the soil The treated soils had bacterial levels 6-40 times
greater than the control chambers.
Over the next four months, the bacterial populations remained fairly
constant in all the organic soil chambers. However, when ethanol and NaOH
treatments were applied to the soil in the T-2 chamber, the population was
lowered by 2-3 orders of magnitude.
Fungal populations in the upper organic soil layer are presented in Table
48. After the spill,the fungal levels decreased slightly in all the organic soil
chambers However, by day 9 the fungal populations had increased substantially.
Fungal populations remained fairly stable through day 183. Small areas of the T-
1 chamber were treated with ethanol-NaOH solutions on day 185 As a result the
fungal populations were reduced to low levels. The entire T-2 organic soil
chamber was treated with ethanol-NaOH solutions on day 210 and as a result the
fungal population was reduced to less than 1000 organisms/g for the remainder of
the experiment.
The bacterial levels in the middle and lower organic soil layers are
presented in Figures C-l and C-2 of Appendix C. The microbial levels in the
middle layers were reduced slightly in the first two days after the spill. The
microbial populations then recovered in the next two weeks and remained stable
for four months. The control soil chamber microbial population in the middle
soil layer recovered as rapidly as the treated soil chambers. Bacterial levels
in the lower layer of the organic soil were reduced by about 4 times after the
spill and recovered rapidly. Also after the treatment with the ethanol and NaOH
solutions, the levels did not fall off as much as the top and middle layers
The bacterial levels in the top layer of the sandy soil are presented in
Figure 33 They decreased from 1/3 to 1/7 of the original levels in the first two
days after the Ethion spill The populations then recovered over the next 2-3
weeks The bacteria in the T-2 chamber had levels 10 times greater than the other
chambers. Over the next four months, the bacterial levels in the treated
chambers were typically greater than the control chamber. The higher bacterial
populations in the treated soil were probably due to the nutrients that were
added. Once again, when the ethanol and NaOH solutions were applied, the
population decreased by 2-3 orders of magnitude
145
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A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED
B. T-1 AND T-2, LIMED, T-2 PLOWED
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH
D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
E. T-1 AND T-2, ETHANOL-WATER SOLUTION
F. T-2, ETHANOL-NaOH SOLUTION
100,000,000
10,000,000
az
ui
£L
1,000,000
UJ
m
s:
ID
z
100,000
O CONTROL
~ TREATMENT 1
A TREATMENT 2
O
<
CD
O-
230 240 250
DAYS
Figure 32. Upper Level organic soil bacterial populations - Ethion spill.
-------
TABLE 48 UPPER LAYER FUNGAL COUNTS (X104/gram of soil) - ETHION SPILL
DAY
SolL Type
and Treatment
In it lal
1
2
9
16
23
30
37
44
52
59
Organic Soli
Control
5.6
.
4.6
188.0
175.0
75.0
33.0
267.0
117.0
28.8
86.7
T-1
5.6
2.7
2.9
275.0
57.0
33.0
10.8
5ft.8
17.0
89.0
48.0
T-2
5.6
-
9.8
73.0
270.0
-
38.0
12.3
32.4
20.0
12.9
Sandy Soil
ConL rol
66.7
2.2
3.6
-
173.0
50.0
52.0
70.0
141.3
80.0
77.5
T-1
66.7
5.2
1.9
80.0
267.0
140.0
140.0
180.0
175.0
46.4
62.5
r-2
66.7
5.7
7.1
385.0
650.0
87.0
50.0
617.0
725.0
54.3
29.2
Clay Soil
Cont rol
22.0
3.3
16.7
110.0
81.0
43.0
70.0
14.0
18.0
115.0
21.0
T-l
22.0
5.0
5.0
78.0
88.0
125.0
115.0
40.0
20.6
85.7
13.1
T-2
22.0
5.4
7.5
330.0
363.0
33.0
350.0
20.0
13.0
47.5
47.9
(continued)
-------
TABLE 48 (continued)
¦p-
CO
anJMeaLnt 6S 7? 79 86 101 108 113 121 127_ 136 155
Control S011 40.7 27.5 310.0 113.0 86.3 78.8 116.0 180.0 129.0 290 0 242 0
T-l 60.0 63.8 150.0 106.0 163.0 52.0 66.7 172.2 7.7 56.5 615.0
t-2 25.5 26.2 100.0 17.J 23.0 25.0 17.0 38.8 22.5 355.0 378.0
Control"11 86.1 55.0 10.0 150.0 275.0 110.0 11.0 258.0 103.0 482.0 1420.0
T-l 129.0 317.0 250.0 400.0 333.0 157.0 167.0 192.0 57.0 2462.0 1340.0
t-2 89.4 67.3 80.0 66.7 82.5 180.0 98.8 81.9 24.5 88.5 1250.0
Cone rol*1 73.1 '6.2 62.8 118.0 20.0 70.0 100.0 78.0 25.0 91.0 102.0
r-1 29.4 70.0 22.4 128.0 263.0 83.0 129.0 - 72.0 393.0 178.0
T-2 36.7 53.8 95.0 77.5 85.0 55.7 131.4 36.0 - 530.0 1310.0
(continued)
-------
TABLE 48 (continued)
Soil Type
and Treotmcnt 159 163 183 187 205 212 220 222 228 238 256
Organic Soli
Control 22.73 57.9 32.5 23.5 66.9 18.0 129.6 40.9 50.0 26.3 41.8
T-l 14.30 26.1 75.9 .97 1.1 0.8 0.68 3.67 0.24 - 1.75
T-2 8.96 338.3 60.3 17.97 97.9 2.0 - - 0.0045 0.053 0.0045
Sandy Soli
Control 3.7 191.4 68.9 29.4 131.1 240.0 - 86.4 1.2 142.6 44.7
I
T-l 235.8 254.0 1175.0 .68 40 7.0 0.076 1.43 1.8 - 0.13
T-2 6.12 2826.0 393.0 298.0 208.0 - 20.0 - 0.015 - 0.032
Clay Soil
Control 3.01 43.8 74.0 235.0 3.02 tntc 9.18 - - 2.34 11.7
T-l 0.67 4.73 12.8 .026 0.43 0.13 0.385 1.31 0.467 0.972 0.473
T-2 55.7 1799.0 160.0 36.0 208.0 - 0.068 - 0.017
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED
B. T-1 AND T-2, LIMED, T-2 PLOWED
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH
D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
E. T-1 AND T-2, ETHANOL-WATER SOLUTION
F. T-2, ETHANOL-NaOH SOLUTION
6 CONTROL
0 TREATMENT 1
A TREATMENT 2
10,000,000
100,000
110
130
170
190
230
250
10
50
A
8 C
D
E
F FF
DAYS
Figure 33. Upper level sandy soil bacterial populations - Ethion spill.
-------
The upper sandy soil layer fungal populations are presented in Table 48. The
fungal population in the top sandy soil layer decreased to about 1/10 of their
original levels in the first two days after the spill. The fungal population
recovered over the next two to three weeks. During the next four months, the
fungal populations remained fairly stable, with no differences between the
control and treated chambers. When the ethanol and NaOH solutions were applied
to the soil, the populations in the treated soils were reduced by two orders of
magnitude.
The bacterial levels in the middle and lower sandy soil layers are presented
in Figures C-3 and C-4 of Appendix C. In the middle soil layer, the microoial
levels decreased 1/3 to 1/2 their initial values in the first two days after the
spill. During the next four months, the populations were relatively constant.
When the ethanol and NaOH solutions were added to the T-2 chamber, the population
decreased by 2-3 orders of magnitude
After the Ethion spill, the bacterial levels in the lower sandy layers
decreased to 1/2 to 1/5 of their original values. Microbial levels remained
relatively steady over the next four months. When the ethanol and NaOH solutions
were added to the soil in the T-2 chamber, bacterial levels decreased by about
1/2. Fungal levels in the T-2 chamber were not different from the populations in
the control and T-l chamber.
The bacterial populations in the top level of the clay soils are presented
in Figure 34. The populations decreased to 1/4 to 1/25 times their original
values after the Ethion was spilled on the soil. During the next 2-3 weeks, the
bacterial populations recovered. The populations in the T-l and T-2 chambers
were significantly higher than the control chamber over the next four months.
The treatments of nutrient broth and pH adjustment were probably responsible for
the greater bacterial populations in the treated chambers. Once again, when the
ethanol and NaOH solutions were added, the bacterial populations in the treated
chambers decreased by 2-3 orders of magnitude. Fungal populations in the upper
clay soil layer are presented in Table 48. Fungal populations decreased to 1/4
to 1/2 of their original levels in the first two days after the spill. The
populations recovered by the 16th day and remained relatively stable for the next
four months. When ethanol and NaOH solutions were added to the treated chambers
the fungal populations decreased by 2-4 orders of magnitude.
The clay soil middle and lower layer bacterial populations are presented in
Figures C-5 and C-6 of Appendix C. Middle layer bacterial levels decreased to 1/2
to 1/4 of the original levels in the first two days after the Ethion spill Fungal
levels, however, were not consistant in their response to the Ethion spill. Both
bacterial and fungal levels remained relatively constant over the next four
months. When the treated chambers received the ethanol and NaOH solutions, the
levels dipped by 2-3 orders of magnitude. The microbial levels in the lower clay
soil layer decreased to 1/3 of their original values after the Ethion was spilled
on the soil. The populations remained fairly stable over the next four months.
When the ethanol and NaOH solutions were applied to the treated chambers, the
microbial levels decreased by about 2 orders of magnitude.
151
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T~2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
© CONTROL
~ TREATMENT 1
A TREATMENT 2
< 10,000,000
K
CD
Q.
00
1,000,000
_l
100,000
10,000
110
130
150
170
190
230
250
A
B C
D
E
F FF
DAYS
Figure 34. Upper level clay soil bacterial populations - Ethion spill.
-------
Soil Ethion Levels
The Ethion levels in the top layers of the organic, sandy and clay soils as
a function of time after the spill are shown in Figures 35-37. The erratic Ethion
concentrations in the soils were due primarily to variation in soil moisture
levels which influenced the percentage recovery. The apparent increase in the
Ethion levels after day 155 was the result of improved extraction procedures.
The extraction procedure which was used after day 155 is detailed in the
Analytical procedures part of Section 7.
Discussion of Results
In contrast to monochlorobenzene, Ethion did not have an immediate effect on
the grass. The grass in all chambers remained healthy for about 1 month after the
spill. The vegetation then slowly wilted and turned brown. During the first five
months after the spill, the Ethion levels in the soils gradually decreased. The
initial treatments, with nutrients or nutrients with aeration, on day 3, were not
effective in significantly increasing the degradation rate of Ethion by
indigenous microorganisms. Adjustment of soil pH on day 44, day 46 and day 53
also did not improve the Ethion degradation rate.
The microbial populations were sufficiently high in the treated chambers
It appeared the microbes were capable of living in the presence of Ethion.
However, either the organisms were incapable of degrading the Ethion or the
Ethion was unavailable to the organisms. Two methods were tried to improve the
water solubility of Ethion and thus its availability to the microbial popula-
tions, i.e., the addition of a surfactant (Tween 80) and the addition of ethanol.
These treatments were applied to the T-l and T-2 chambers on day 95 and day 122,
respectively. These treatments did not improve the Ethion degradation rate by
microorganisms.
Iwata et al (1975) found Ethion to be a persistent organophosphorus
pesticide. In their studies, only 28% of the Ethion was removed from the soil in
a 200 day period. They calculated the half-life of Ethion in soils to be 420 days.
Our data show that 51% of Ethion was removed from the organic soil in 162 days.
The percent Ethion removed from the sandy and clay soils over the same period were
43 and 60%, respectively. The half-lives of Ethion assuming a first order decay
in the three soil types were calculated to be:
157 days - organic
200 days - sandy
123 days - clay
On day 210, day 219 and day 220, the T-2 chambers were treated with a total
of 10 liters each of a 50-50 ethanol-water solution containing 6.8% sodium
hydroxide The purpose of this treatment was to determine if the Ethion could be
hydrolyzed in the soil The pH of the top layer of soil was raised to 10-12 by
this treatment. Due to the high pH, microbial levels dropped drastically. In the
organic soil, the hydrolysis treatment reduced the Ethion levels from 55,000 ppm
to less than 4,000 ppm. Ethion levels in the top layer of the sandy soil
decreased from approximately 60,000 ppm to less than 10,000 ppm. The Ethion
levels in the clay soil were not substantially affected by the treatment.
153
-------
y—
H.
~H
B.
C.
3
>-
OH
130,000
a.
n
120,000
_
V
110,000
-
CO
7-
100,000
-
O
90,000
-
80,000
-
oc
70,000
-
z
60,000
-
«_)
50,000
-
o
AO,000
-
30,000
-
o
20,000
_
I
10,000
_
1—
11J
0
1 1
T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D.
T-1 AND T-2, LIMED, T-2 PLOWED E.
T-1 AND T-2, LIMED AND NUTRIENT BROTH F.
T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
T-1 AND T-2, ETHANOL-WATER SOLUTION
T-2, ETHANOL-NaOH SOLUTION
© CONTROL
0 TREATMENT 1
A TREATMENT 2
DAYS
Figure 35. Upper level ethion concentrations in organic soil.
-------
on
a
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D.
B. T-1 AND T-2, LIMED, T-2 PLOWED E.
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F.
T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
T-1 AND T-2, ETHANOL-WATER SOLUTION
T-2, ETHANOL-NaOH SOLUTION
a. 120,000
110,000
« 100,000
z
o
Q1
o
M
X
90,000
80,000
70,000
60,000
50,000
AO,000
30,000
20,000
10,000
0
CONTROL
TREATMENT 1
TREATMENT 2
I ¦ I ¦ 1 ¦ I ¦ I
180 190 200 ijpOll 230
F FF
10 20 30 AO
60 70 80 90 1100 11
130 1 AO 150 160
DAYS
Figure 36. Upper level ethion concentrations in sandy soil.
-------
X
KD
Ln
ON
o_
Q_
C
en
z
LU
90,
80,
70,
60,
50,
AO,
30,
20,
10,
A.
B.
C.
000
000
000
000
000
000
000
000
000
0
T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D.
T-1 AND T-2, LIMED, T-2 PLOWED E.
T-1 AND T-2, LIMED AND NUTRIENT BROTH F.
T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
T-1 AND T-2, ETHANOL-WATER SOLUTION
T-2, ETHANOL-NaOH SOLUTION
O CONTROL
~ TREATMENT 1
A TREATMENT 2
I l |_j I i I i I i I i I i I I L_i I i I i I i I i I i I i L_j 1 i J i I l
4cl | 60 80 |l00 13p 140 160 130 200 j
B C
D E
DAYS
F FF
Figure 37. Upper Level ethion concentrations in clay soil.
-------
Following treatment with sodium hydroxide and ethanol, a number of
tentative degradation products were observed by gas chromatography/mass spec-
troscopy. None of the observed peaks could be matched to entries in the N1H/EPA
Mass Spectral Search System (MSSS). Tentative molecular formulae and possible
structural assignments for several the peaks are presented in Table 49 However,
confirmation of identity without isolation of sufficient material for NMR and IR
spectra is not possible. The tentative structures are consistant with products
which might be expected from multiple nucleophilic displacements For example,
the most abundant product "B" could be formed by the following route:
c2h5-qJ ^ V-C2H5 c2h5-o s
p-s-ch2—s-p )P-S©
c2H5~o/ ^oh® o-c2h5 c2h5-o
c2h5-o
CH3-CH2-t> f $/P-c2h5
r ^-S-CH2-S-Pn
CI'3"CH2-0/ 0-C2H5
c2h5-0 s
;p-s-c2h5
c2h5-o
Radiation Levels
The radiation levels in the top layers of the organic, sandy and clay
soils are compiled in Figures C-7, C-8 and C-9 of Appendix C. The radiation
levels in all soils were variable but indicate a loss of activity over time.
After the ethanol-NaOH solution treatment, the radiation levels in the T-2
chambers did not decrease significantly. These results indicated that the S-CH2-
S-carbon in the center of the Ethion molecule (the labelled site) was still
present in the soil.
Regression lines, by the least squares method, were fit to the net
levels in the soils to give a percentage lost over time A first order decay was
used to give the following half-life estimates for Ethion.
162 days - Organic soil
117 days - Sandy soil
159 days - Clay soil
The time period was for days 65 to 220, or over a 155 day period. Except for
the sandy soil, the radiation half-lives agree fairly well with the half-lives
determined from Ethion levels.
157
-------
TABLE 49. ETHION RELATED RESIDUES
Peak
Molecular
Ion
Base
Suggested
Formulae
Possible Structure
A
198
121
C6H15PO3S
5
t(0-CH2CH3)3
B
214
186
C6H15PO2S2
S
CH3CH2-s4(OCH2CH3)2
C
214
125
C6H15PO2S2
0
CH3CH20£(S-CH2CH3)2
D
260
121
C7H17PO2S3
S
(CH3CH20)2i)-S-CH2-S-CH2CH3
E
338
245
CgH2op2°4s3
f ?
(CH3CH20)2-P-S-P-(C0H2CH3)2
F
296
81
c6H15p2°5s2
S 0 OCH2CH3
(CH3CH2O)2p-s-£ Coh
G
384
231
C9H22p2°4s4
Ethion
158
-------
LAND RESTORATION TECHNIQUE II - FORMALDEHYDE SPILL
Soil pH
The soil pH values as a function of core depth over the test period for the
organic, sandy and clay environmental chambers are presented in Tables D-2, D-3
and D-4 of Appendix D. The organic soil was initially neutral in pH. The first
four days after the spill, the upper layer of the soil was basic. However, the
soil then became acidic, leveling off at a pH in the 5.3-6.2 range. On days 52
and 64, lime was added to the treatment-1 and -2 chambers to raise the pH. The top
soil layers of these chambers reached a pH of 6.3-6.4
The sandy soil was initially slightly acidic. Through the first four days
after the spill, the soil was slightly basic. The pH leveled off at a pH range
from 4.3-5.8. Lime was added to the treatment-1 and -2 chambers on days 52 and
64 raising the pH in the top layer of soil to 6.0.
The clay soil initially had an acidic pH. The first two days, after the
spill, the pH levels increased to a neutral pH. The pH then decreased to a range
from 4.4-5.9. Lime was added to the treatment-1 and -2 chambers on days 52 and
64 raising the pH in the top layer of soil to 5.1-5.5.
Soil Moisture Content
The percent moisture data of the soils are presented in Tables D-5, D-6 and
D-7 of Appendix D. The organic soils had the highest moisture levels, typically
in the 20-30% range The sandy and clay soils were slightly drier with a typical
moisture range from 15-25%. Throughout the experiment, the moisture levels
remained relatively stable and did not substantially alter the microbial levels
in the soil.
Microbial Populations
The bacterial populations in the top layers of the organic, sandy and clay
soils are presented in Figures 38-40. Middle and lower soil layer microbial
populations are presented in Figures D-7 to D-12 of Appendix D.
The bacterial count in organic soil was reduced 2 to 3 orders of magni-
tude after the addition of formaldehyde. By day 56, the bacterial levels in
the top soil layer had recovered. Fungal populations in the upper organic
soil layer are presented in Table 50. Fungal populations decreased by 3 or-
ders of magnitude in the first 2 days after the spill. The population levels
gradually increased over the test and approached their pre-spill levels by the
end of the experiment. The middle and lower soil bacterial levels recovered
earlier than the upper soil layer. Middle soil bacteria levels were near pre-
spill population densities by the 18th day. The bacteria in the lower soil
layer recovered to the pre-spill levels by the 15th day. Fungal levels in the
middle and lower soil layers reached their pre-spill numbers by the 22nd day,
as shown in Figures D-7 and D-8.
159
-------
100,000,000
CONTROL
~ TREATMENT 1
A TREATMENT 2
10,000,000
s:
UJ
£
o
A. T-1, PRIMARY SEWAGE EFFLUENT
T-2, PRIMARY SEWAGE EFFLUENT
CULTURED WITH 5000 PPM
FORMALDEHYDE
8. T-1, T-2, LIME ADDED
i-
100,000
a.
o
10,000
60
65
20
30
40
45
TIME IN DAYS
Figure 38. Upper level organic soil bacterial populations
- formaldehyde spill.
-------
CONTROL
TREATMENT 1
TREATMENT 2
1,000,000--
A. T-1, PRIMARY SEWAGE EFFLUENT
T-2, PRIMARY SEWAGE EFFLUENT
CULTURED WITH 5000 PPM
FORMALDEHYDE
B. T-1, T-2, LIME ADDED
10,000
1,000
10
20
30 35
TIME IN DAYS
60
65
70
40
50
A
A
B
B
Figure 39.
Upper level sandy son I bacterial populations - formaldehyde spill.
-------
10,000,000 -H
G CONTROL
0 TREATMENT 1
A TREATMENT 2
1,000,000 - =
100,000 --
to
OL
UJ
CO
Z
o
t—<
(-
c
10,000 --
A. T-1, PRIMARY SEWAGE EFFLUENT u
T-2, PRIMARY SEWAGE EFFLUENT CULTURED
WITH 5000 PPM FORMALDEHYDE
B. T-1, T-2, LIME ADDED
a.
o
a.
1,000
20
-5
30 35
45
50
60
65
70
AO
B
A
A
B
TIME IN DAYS
Figure 40. Upper Level clay soil bacterial populations - formaldehyde spill.
-------
TABLE 50. UPPER LAYER FUNGAL COUNTS (X102/gram soil) - FORMALDEHYDE SPILL
DAY
Soil Type
and Treatment
Initial
1
2
4
5
7
9
11
15
18
Organic
Control
2850.0
7.1
3.2
1.43
217.0
28.6
110.0
158.0
150.0
T-l
2830.00
1.05
4.0
77.0
25.0
320.0
40.0
12.5
110.0'
14.3
T-2
2850.0
9.0
19.0
20.0
2.0
300.0
50.0
22.0
129.0
50.0
Sandy Soil
,Control
13600.0
5.6
32.0
5.0
3.33
62.5
20.0
66.7
45.0
11.1
T-L
|
13600.0
29.0
23.0
9.5
12.5
33.3
-
8.3
58.0
57.1
T-2
13600.0
-
-
71.40
25.0
25.0
143.0
9.0
110.0
62.5
Clay Soil
Control
2550.0
2.0
2.9
1 '.G
10.0
25.0
9.0
-
60.0
14.3
T-l
2550.0
1.4
6.1
4.0
.90
12.5
-
16.7
50.0
-
T-2
2550.0
15.0
.68
14.0
11.1
1400.0
-
-
492.0
14.3
(continued)
-------
TABLE 50 (continued)
DAY
Soil Type
and Treatment
22
25
28
32
36
4 2
49
56
66
70
Organic
Control
T-l
T-2
Sandy Soil
Control
T-l
1-2
Clay Soli
Control
T-l
T-2
56.0
106.0
188.0
70.0
20.0
6.3
7.0
22.0
6.7
133.0
200.0
138.0
90.0
3.3
25.5
17.0
2.0
63.0
700.0
50.0
21.0
2.2
44.0
1.1
50.0
1210.0
267.0
250.0
260.0
1000.0
4.0
107.0
2630.0
210.0
1000.0
470.0
11.0
120.0
70.8
7.5
293.0
3080.0
63.0
300.0
50.0
50.0
2.5
3.1
569.0
1230.0
114.0
133.0
1556.0
30.0
14.40
72.9
29.4
130.0
2640.0
155.0
130.0
tntc
193.0
0.66
1.6
200.0
6250.0
1310.0
10660.0
33.0
73.0
65.0
1.6
1490.0
2500.0
33.0
920.0
260.0
150.5
51.0
25.7
19.8
260.0
11800.0
-------
After the spill, the bacterial levels in the sandy soil chambers were
reduced by 2-3 orders of magnitude. Bacterial levels in the upper soil layer were
similar in all the chambers for the first 25 days. When the second microbial
treatment was applied on day 25, the bacterial numbers in the upper and middle
levels of the treatment-1 chamber increased rapidly to pre-spill populations.
The treatment-2 and control chambers did not have similar increases in bacterial
levels.
The fungal populations in the upper sandy soil layers are presented in Table
50 The fungal numbers per gram in the sandy soil decreased by 2-3 orders of
magnitude after the spill. The fungal counts did not increase to the pre-spill
levels during the test. In addition, no definite trends were observed in fungal
counts after the treatments were applied
Bacterial populations were reduced by 2-3 orders of magnitude in the upper
layer of the clay soils by the formaldehyde spill. In the middle and lower
layers, however, microbial levels were reduced by about one order of magnitude.
Bacterial counts in the upper soil layer of all chambers were approximately the
same over the first 25 days after the spill. After the second microbial treatment
on day 25, the bacterial counts in the upper layer of chamber T-2 were higher than
the control and T-l chambers. The fungal populations in the upper clay soil layer
are presented in Table 50 Fungal populations decreased by 3 orders of magnitude
in the first two days after the spill. By day 32 the T-l and T-2 chambers had
fungal populations 1-3 orders of magnitude greater than the control.
In the middle soil layer, the control chamber bacterial levels were higher
than those of T-l and T-2 chambers. The middle layer fungal populations in the
T-2 chamber increased after the treatment on day 25. Microbial levels in the
lower soil level exhibited no trends during the test.
The recovery time of the microorganisms in the clay soils increased with
depth. In the upper soil layer in chamber T-2, the bacteria reached pre-spill
levels on day 49 as did the fungi on day 32. The other chambers either reached
pre-spill levels at the end of the test or not at all.
Soil Formaldehyde Levels
The formaldehyde concentrations in the top soil layer are plotted versus
time in Figures 41-43. The radiometric data in the upper soil layers are plotted
in Figures D-13, D-14 and D-15 of Appendix D. The formaldehyde concentrations in
the middle and lower soil layers are presented in Figures D-l through D-6 of
Appendix D. Generally, there was a rapid loss of formaldehyde from the upper soil
layer in all chambers during the first 10 days A concurrent drop in pH levels
in the soil indicate that formaldehyde is oxidized to formic acid by microbial
action or chemical reaction with soil constituents. The formaldehyde concen-
trations then decreased at a slower rate during the next 25-30 days. During this
time period, bacterial levels slowly increased, thus indicating the build-up of
formaldehyde metabolizing and formaldehyde resistant colonies.
Discussion of Results
The spill of formaldehyde was toxic to both the microorganisms in the soil
165
-------
10,000 -I
§: 1,000 --
o
t/i
tn
z
c
<
C£
I-
z
UJ
u
a
>-
a
_J
q:
o
100 --
10.
1"
O CONTROL
~ TREATMENT 1
^ TREATMENT 2
ADDED
55 60
A. T-1 -PRIMARY SEWAGE
EFFLUENT
T-2 - PRIMARY SEWAGE
CULTURED WITH 5000 PPM
FORMALDEHYDE
T-1, T-2 - LIME
of 5
A
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Figure 41. Formaldehyde concentrations in upper Layer of organic soils.
166
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167
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168
-------
and the plant life. Visible inspection of the chambers indicated that the grass
was dead by the end of the second day after the spill.
In the organic soils, formaldehyde concentrations in the treated and
control chambers were essentially the same for the first 25 days. The second
microbial treatment applied on day 25 was again ineffective in accelerating the
removal of formaldehyde from the soil as can be seen by comparing this
formaldehyde removal rate with that observed in the control. The radiometric
data in general confirms the formaldehyde analyses (See Figures D-13, D-14 and D-
15 of Appendix D).
It appears that the microbial populations in both the control and treated
chambers gained viability at approximately the same time This recovery occurred
when formaldehyde levels decreased to approximately 1000 ppm. Once the microbial
population regained stability, the formaldehyde levels in the soil decreased
rapidly. Thus, it appears that high formaldehyde concentrations (greater than
1000 ppm) are toxic to the soil microbial populations. However, once the
formaldehyde is reduced to tolerable levels, the organic soil provides adequate
nutrients for microbial metabolism.
The sandy soil upper layers exhibited only slight differences in for-
maldehyde levels between treated and control chamber over the initial 25 days
(Figure 42) However, after the second treatment was applied on the 25th day,
both treatment-1 and -2 soils had lower formaldehyde levels than the control.
The T-l chamber, treated with the unadapted primary sewage effluent, had the most
rapid loss of formaldehyde. The middle sandy soil layers of the three chambers
(Figure D-3) had approximately the same formaldehyde concentrations for the
first 20 days. However, the formaldehyde concentrations in T-l and T-2 continued
to decline from day 20-66, while the concentration in the control chamber
remained relatively stable. The treated and control chambers had no significant
differences in formaldehyde concentrations at the lower level. The concentra-
tions gradually declined throughout the study.
The formaldehyde levels in the upper layer of all the clay soil chambers
were approximately the same during the first 25 days after the spill. The second
treatment of microorganisms (day 25) increased the rate of depletion of the
formaldehyde in the treated chambers. The T-2 chamber, receiving the Pseudomonas
sp. culture had a faster rate of disappearance of formaldehyde concentration than
in the T-l chambers. However, the rate of disappearance of formaldehyde in the
control chamber remained constant. By the 47th day, both treated chambers had
upper layer formaldehyde concentrations less than 100 ppm, while the control
chamber contained over 1000 ppm of formaldehyde in the soil.
The middle soil layer in the clay chambers had initial formaldehyde
concentrations between 500-1000 ppm. The T-2 chamber middle layer reached 0 ppm
of formaldehyde on day 52. The lower clay soil layers (Figure D-6) showed no
significant trends in formaldehyde concentration that could be attributed to the
treatments used All lower clay layers had formaldehyde concentrations less than
30 ppm on the 46th day
169
-------
Regression lines were fitted to the formaldehyde data from the upper soil
layers by the least-squares method. The slopes, or rate of loss of formalde-
hyde, are presented in Table 51. Regression lines were also fitted to the
net counts per minute versus time. The slopes of these lines are presented in
Table 52.
The higher rate of removal of formaldehyde from the sandy T-l and clay
T-2 chambers correlates with the loss of -^C activity in the chambers.
LAND RESTORATION TECHNIQUE II - ANILINE SPILL
Soil pH
The soil pH values for the organic, sandy and clay soils with core depth
over time are presented in Tables E-2, E-3 and E-4 of Appendix E. The pH lev-
els in the upper level organic soil control and T-l chambers remained fairly
stable with the majority of the values between 7 and 7.5. The T-2 chamber, pH
values in the upper layers were typically between 6 and 7.
TABLE 51. RATE OF FORMALDEHYDE LOSS (PFM/DAY)
Soil Types
Chamber
Organic
Sandy
Clay
Control
145
82
48
T-l
110
90
64
T-2
122
51
72
TABLE 52. LOSS RATE OF C-14 ACTIVITY (NET CPM/DAY)
Chambers
Soil Types
Organic
Sandy
Clay
Control
2.3
1.3
0.7
T-l
4.5
1.1
1.0
T-2
1.8
0.5
1.0
170
-------
Sandy soil pH levels had trends similar to those measured in the organic
soil chambers. The control chamber sandy soil had near neutral pH values,
typically between 6.9 and 7.3. The T-l chamber soil pH levels were more acidic
with the majority of the values between 6.3 and 6.8. The typical soil pH values
in the T-2 chamber ranged from 5.5-6 6.
The clay soil pH values in the control chamber were erratic and pre-
dominantly acidic. The T-l chamber soil pH values typically ranged between 5.5
and 6.3. The majority of the soil pH values in the T-2 chamber ranged between 5.8
and 6.9.
Soil Moisture Content
The percent moisture as a function of depth and time for the organic, sandy
and clay soils are presented in Tables E-5, E-6 and E-7 of Appendix E. For the
organic soil chambers, there were no significant differences in moisture levels
between chambers. The typical upper layer moisture content ranged between 23 and
36%. The typical upper layer moisture content in the sandy soil chambers ranged
from 20 to 28% The majority of the clay soil upper layer moisture content values
ranged from 12 to 20%.
Microbial Populations
The soil bacterial populations in the upper layers of the organic, sandy,
and clay soils as a function of time are presented in Figures 44-46.
Bacterial levels in the upper layer of the organic soil decreased by a
factor of 10 after the aniline spill. The bacterial populations in all the
chambers were relatively similar for the next ninety days. After the treatment
with the mixed microbial population on day 96, the bacterial levels in the T-l
chamber were approximately ten times higher than the control chamber for the
remainder of the experiment.
After the aniline spill, bacterial levels decreased in the upper layers of
the sandy soils decreased by factors of 4 to 50. The bacterial levels in the
control and T-l chambers gradually increased over the remainder of the
experiment The bacterial levels in the T-2 chamber decreased by about 10 times
after the addition of 15% hydrogen peroxide on day 42. The bacterial population
in the T-2 chamber gradually recovered and by day 120 were similar to the other
sandy soil chambers.
The bacterial levels in the clay soil decreased by 10-100 times after the
aniline spill. The bacterial population recovered after about 30 days. After day
60, the bacterial levels in chamber T-l were greater than the control and the
control bacterial levels were greater than the chamber T-2.
Soil Aniline Levels
The aniline concentrations versus time for the upper layers of the organic,
sandy, and clay soils chambers are presented in Figures 47-49. The aniline
concentrations in the middle soil levels are presented in Table E-8 of Appendix
E
171
-------
A. T-2 15% H202, T-1 AND T-2 PRIMARY SEWAGE EFFLUENT
B. T-2 15% H202
C. T-1 PRIMARY SEWAGE EFFLUENT AND NUTRIENT BROTH
D. T-1 MIXED MICROBIAL CULTURE AND NUTRIENT SALTS
E. T-1 NUTRIENT SALTS AND YEAST EXTRACT
F. T-2 NUTRIENT SALTS AND YEAST EXTRACT
a:
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Figure 44.
Upper level organic soil bacterial populations - aniline spill.
-------
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C. T-1 PRIMARY SEWAGE EFFLUENT
AND NUTRIENT BROTH
D. T-1 MIXED MICROBIAL CULTURE
AND NUTRIENT SALTS
E. T-1 NUTRIENT SALTS AND YEAST
EXTRACT
F. T-2 NUTRIENT SALTS AND YEAST
PPF. . ¦ i
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DAYS
110 120
140 1501 160
130
Figure 45. Upper level sandy soil bacterial populations - aniline spill.
-------
A. T-2 15% H2O2, T-1 AND T-2 PRIMARY SEWAGE EFFLUENT
B. T-2 15% H202
C. T-1 PRIMARY SEWAGE EFFLUENT AND NUTRIENT BROTH
D. T-1 MIXED MICROBIAL CULTURE AND NUTRIENT SALTS
E. T-1 NUTRIENT SALTS AND YEAST EXTRACT
F. T-2 NUTRIENT SALTS AND YEAST EXTRACT
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Figure 46. Upper level clay soil bacterial population - aniline spill.
-------
T-2 15% H202, T-1 AND T-2 PRIMARY SEWAGE EFFLUENT
T-2 15% H202
T-1 PRIMARY SEWAGE EFFLUENT AND NUTRIENT BROTH
T-1 MIXED MICROBIAL CULTURE AND NUTRIENT SALTS
T-1 NUTRIENT SALTS AND YEAST EXTRACT
T-2 NUTRIENT SALTS AND YEAST EXTRACT
O CONTROL
~ T-1
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50,000 --
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Figure 47. Aniline concentrations - upper level of organic soil.
-------
A. T-2 15% H202, T-1 AND T~2 PRIMARY SEWAGE EFFLUENT
B. T-2 15% H202
C. T-1 PRIMARY SEWAGE EFFLUENT AND NUTRIENT BROTH
D. T-1 MIXED MICROBIAL CULTURE AND NUTRIENT SALTS
C. T-1 ilUTRIENT SALTS AND YEAST EXTRACT
F. T-2 NUTRIENT SALTS AND YEAST EXTRACT
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A. T-2 15% H202, T-1 AND T-2 PRIMARY SEWAGE EFFLUENT
B. T-2 15% H202
C. T-1 PRIMARY SEWAGE EFFLUENT AND NUTRIENT BROTH
D. T-1 MIXED MICROBIAL CULTURE AND NUTRIENT SALTS
E. T-1 NUTRIENT SALTS AND YEAST EXTRACT
F. T-2 NUTRIENT SALTS AND YEAST EXTRACT
O CONTROL
O TREATMENT 1
A TREATMENT 2
20,000
15,000
10,000
5,000
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F
DAYS
Figure 49. Aniline concentrations - upper level of clay soiL.
-------
Discussion of Results
The aniline spill was toxic to soil microbes and plants. The grasses in the
chamber were dead by the end of the fourth day after the spill.
The initial treatments with hydrogen peroxide and primary sewage effluent,
T-2, or primary sewage effluent alone, T-l, were relatively ineffective in
reducing aniline levels in the organic soil. However, on day 96, the T-l chamber
was treated with a mixed culture of microorganisms and a nutrient salt solution.
By day 113, the aniline levels in the T-l chambers were significantly lower than
the control chamber. The addition of nutrient salt and yeast extract solutions
on day 126 and 154 continued to reduce the aniline levels in the T-l chamber. By
day 160, aniline levels in the T-l chamber were less than 100 ppm. The treatments
applied to the T-2 chamber were not effective in reducing the aniline concentra-
tions in the soil.
The hydrogen peroxide treatments reduced the aniline concentrations in the
T-2 sandy chamber by 20-40%. The T-2 chamber had the lowest aniline con-
centrations for the remainder of the experiment. The initial addition of primary
sewage effluent (treatment-1) to the sandy soil chamber was ineffective.
However, after the addition of the mixed microbial culture and the nutrient salts
on day 96, the aniline level decreased by 6000-8000 ppm Another decrese in the
soil, aniline concentration in the T-l chamber was observed after the nutrient
salts and yeast extract were added on day 154.
None of the treatments were effective in accelerating the removal of aniline
from the clay soil Aniline levels in all three chambers decreased at a similar
rate.
Half-lives of aniline concentrations in the organic and sandy soils are
presented in Table 53. The half-lives were calculated assuming a first order
decay. For the organic soil, the aniline concentration in the control chamber on
day 12 was used as the initial value for the calculations. The half-life of
aniline in the T-l chamber was about 1/2 the half-lives in the control and T-2
chambers.
The half-lives for the sandy soil chambers were separated in parts. In
the first part of the experiment (days 7-91), the T-2 chamber which received
hydrogen peroxide had the shortest half-life. However, in the second part of
the experiment (days 91-166), the T-l chamber had the shortest half-life. The
T-l chamber received the adapted mixed microbial culture and nutrient salts
during this period.
TABLE 53. HALF-LIVES OF ANILINE IN ORGANIC AND SANDY SOILS
Organic
Soil
Sandy Soil
Chamber
Days 12-
•166
Days 7-
-91 Days 91-166
Control
44
39
45
T-l
19
63
24
T-2
58
28
49
1.78
-------
LAND RESTORATION TECHNIQUE III - CHLORDANE SPILL
Soil pH
The data on the soil pH levels as a function of depth and time, for the
chlordane experiment, are presented in Table F-2 or Appendix F. All the T-2
chambers, which received the lime, had pH levels from 7.3-9.2. The organic and
sandy soil control chambers had near neutral pH values, while the control clay
soil chamber had pH values near 9. The T-l chambers organic soil had pH values
near neutral, the sandy soil had pH values near 8 and the clay soil had acidic pH
levels.
Soil Moisture Content
The data on the percent moisture levels in the soils for the chlordane
experiments are presented in Table F-3 of Appendix F. The organic soil moisture
levels ranged from 11-35%. The sandy soil moisture levels ranged from 13-30% and
the clay soil from 10-25%.
Microbial Populations
The chlordane spill did not affect the bacterial populations in the soils.
These populations as a function of time are presented in Table F-4 of Appendix F.
After the spill, bacterial populations increased in all chambers. Generally, the
T-l chambers had the highest bacterial populations.
Soil Chlordane Levels
The chlordane concentrations in the organic, sandy and clay soils as a
function of time are shown in Figures 50-52. The data from the organic and sandy
soils are very erratic The clay data are somewhat better. The erratic data are
due either to bad extraction or non-representative subsamples.
Discussion of Results
The chlordane spill was not significantly toxic to soil microbes. However,
it was toxic to the grass in the chambers. The grass was completely dead within
48 hours after the spill.
In general, there was no loss of chlordane from the clay or the organic
soils. The organic T-l soil showed a slight decline in chlordane, however, the
data are too scattered to draw any definite conclusions. In all sandy soil upper
layers chlordane concentrations decreased. The control and treated chambers
appeared to lose chlordane at a similar rate. The radiation levels in the sandy
soils (see Table 54) also show a gradual decrease in activity No chlordane was
found in the traps or carbon filters or in any of the chambers. The levels
in the bubblers from the sandy chambers were below the detection limits.
From the data, it appears that chlordane is persistent in the soils with the
possible exception of the sandy soils. However, it is not known if the apparent
decrease in chlordane levels was due to degradation or volatilization No
179
-------
T-1 ADDITION OF MICROBIAL CULTURE AND NUTRIENT SALTS
T-2 ADDITION OF LIME, MICROBIAL CULTURE AND NUTRIENT SALTS
O CONTROL
~ TREATMENT 1
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5,000
A, 000
3,000
2,000
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45
50
40
10
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DAYS
Figure 50. Chlordane Concentrations in upper level of organic
soi I.
-------
A. T-1 ADDITION OF MICROBIAL CULTURE AND NUTRIENT SALTS
T-2 ADDITION OF LIME, MICROBIAL CULTURE AND NUTRIENT SALTS
O CONTROL
6,000
~ TREATMENT 1
A TREATMENT 2
5,000
3,000
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Figure 51. Chlordane concentrations in upper Level of
sandy soi I.
-------
A. T-1 ADDITION OF MICROBIAL CULTURE AND NUTRIENT SALTS
T-2 ADDITION OF LIME, MICROBIAL CULTURE AND NUTRIENT SALTS
5,000
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Figure 52. Chlordane concentrations in upper Level of
clay soil.
-------
TABLE 54 1AC RADIATION COUNTS IN SANDY SOILS TREATED WITH 14C - CHLORDANE
Days
Chamber Treatment 1 2 6 13 21 27 33 37 49 175
Control 219 146 137 93 92 56 172 50 77 27
T-l - 223 250 99 101 70 72 83 150 26
T-2 170 168 202 120 109 279 118 194 72 17
-------
degradation products were found in the GC traces, however, column conditions
and/or extraction conditions may have not been favorable for their detection.
LAND RESTORATION TECHNIQUE III - 2,4-DINITROPHENOL SPILL
Soil pH
The soil pH levels in 2,4-dinitrophenol chambers are presented in Table G-
2 of Appendix G. The initial organic soil pH values were near neutral The sandy
and clay initial pH values were acidic. The lime added to the treated chambers
increased the pH of the soil by 2-3 units
Soil Moisture Content
The soil percent moisture data are presented in Table G-3 of Appendix G. The
percent moisture values ranged from 23-34% in the organic soils; 23-32% in the
sandy soils;ll-28% in the clay soils.
Microbial Populations
Soil bacterial populations are presented in Table G-4 of Appendix G. The
addition of the 2,4-dinitrophenol to the soil reduced the bacterial population
by one-half to 100-fold. By the 12th day the bacterial population in the
treated clay soil chamber had recovered to pre-spill levels. However, the or-
ganic and sandy soil bacterial levels did not return to pre-spill levels be-
fore the end of the test.
Soil, 2,4-Dinitrophenol Concentrations
The 2,4-dinitrophenol levels in the organic soil are presented in Figure 53.
The erratic chemical concentration values were in part due to the clumping of the
dinitrophenol after watering of the organic soil. Dinitrophenol conentrations
in the upper layer of both organic soil chambers were less than 2000 ppm on day
62.
The sandy soil 2,4-dinitrophenol concentration-time data are presented in
Figure 54 The dinitrophenol concentrations in the control and treated chambers
decreased a similar rate during the experiment. The 2,4-dinitrophenol concen-
trations were less than 2000 ppm in both chambers after day 22.
The 2,4-dmitrophenol concentrations in the clay soils are presented in
Figure 55. The treated clay soil chamber had 2,4-dinitrophenol levels less than
1000 ppm by the end of the test. If it is assumed that the initial sample from
the control chamber is not representative (both chambers received the same amount
of dinitrophenol), then the treated clay chamber had an accelerated rate of loss
of dinitrophenol from the soil.
Discussion of Results
2,4-Dinitrophenol is a good example of a compound which can produce a
relatively persistent, slightly water soluble chemical spill on land. This
chemical killed the grass cover in the chamber within 5 days after the spill It
also depressed the soil microbial populations.
184
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Figure 53. 2,4-Dinitrophenol concentrations in the upper Level of the organic soils.
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B. ADDITION OF MICROBIAL CULTURE, NUTRIENT SALTS AND YEAST EXTRACT TO TREATED CHAMBER
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Figure 55. 2,4-DimtrophenoL concentrations in the upper Level of the clay soils.
-------
The variation in the 2,4-dmitrophenol concentrations in the organic soil
chambers was due in part to nonrepresentative sampling. Sampling problems were
caused by the clumping of the 2,4-dinitrophenol particles in the organic soil
chambers.
The 2,4-dinitrophenol concentrations in the upper layer of the treated and
control sandy soil chambers are similar throughout the experiment. The 2,4-
dinitrophenol concentrations decrease from near 4,000 ppm at day 1 to 1200-1400
ppm at day 62. The treatments were not effective in increasing the 2,4-
dinitrophenol removal from the sandy soil.
The treated clay soil chamber appeared to have an initial 50% loss of 2,4-
dmitrophenol concentration in the upper layer during the first 12 days. After
day 12 the upper layer 2,4-dmitrophenol concentrations were relatively stable
between 500-1000 ppm. The 2,4-dinitrophenol concentration in the upper layer
clay soil control chamber were near 2000 ppm on day 12 and gradually decreased to
1000 ppm by day 62 After the initial treatment of the microorganisms, the 2,4-
dinitrophenol concentrations in the treated clay soil chamber were reduced by at
least 1000 ppm However, further reductions in the 2,4-dinitrophenol levels did
not occur.
LAND RESTORATION TECHNIQUE IV - CADMIUM. NITRATE AND LEAD NITRATE SPILL
Soil pH
The soil pH levels are presented in Tables H-l and H-2 of Appendix H. The
average pH levels for the organic, sandy, and clay soils were 6.9, 6.0 and 6.6,
respectively, for the cadmium uptake experiment and 6.9, 5.8 and 6.7, respecti-
vely, for the lead uptake experiment.
Soil Metal Levels
Initial and final cadmium and lead soil concentrations are presented in
Table 55. Variations in metal concentrations between soils were primarily due to
soil density. Soil cadmium concentrations decreased during the experiment in all
the chelated soil chambers and in the pH adjusted sandy soil chambers which
contained lettuce and chard. Soil lead concentrations decreased during the
experiment in the treated organic and sandy soil chambers.
Plant Uptake of Metals
The lead levels in the selected plants are presented in Table 56. After the
first collection of plant samples, on day 30, the high lead levels were found in
both the acidic soil and acidic soil plus EDTA chamber plants. The controls had
very low levels of lead. The rye grass had levels of 135 and 85 ppm from the
organic and sandy chelated soil chambers The Kentucky fescue grass had lead
levels of 129 and 88 ppm from the sandy and clay (pH adjusted only) soil chambers.
Stress of the plants was noted in sandy and clay soil chambers Shortly after
emergence, the beet plants died. Swiss chard was then planted to replace the
beets on day 22.
188
-------
TABLE 55 AVERAGE SOIL CONCENTRATIONS OF CADMIUM AND LEAD
Soil Type
Chamber Treatment
Cadmium (ppm, dry weight)
Initial Final
0-5 cm 5-15 cm 0-5 cm 5-15 cm
Lead (ppm, dry weight)
Initial Final
0-5 cm 5-15 cm 0-5 cm 5-15 cm
Organic
Sandy
Clay
Control 3
Meta1/Lettuce, 165
Beets
Metal/Chelated 173
Metal/rye, Kentucky 165
fescue grass
Control 3
Meta1/Lettuce, 86
Beets
Metal/Chelated 108
Metal/rye, Kentucky 58
fescue grass
Control 4
Meta1/Lettuce, 45
Beets
Metal/Chelated 90
Metal/rye, Kentucky 52
fescue grass
3
145
133
179
3
34
110
17
3
64
37
60
3
151
58
158
3
31
51
83
4
47
20
39
3
100
29
10
3
14
55
43
4
8
17
34
4
321
225
261
4
516
267
287
4
169
105
210
4 4
238 286
4
85
255
5
282
60
47
4
139
137
164
208 104
116 156
5
201
148
123
4
305
185
262
42
4
110
69
5
96
100
73
-------
TABLE 56. LEAD LEVELS IN PLANTS AS A FUNCTION OF SOIL TYPE AND TREATMENT
Lead Levels;
Day
Plant Type
Soil Type
Soil Treatment ppm Dry Weight
30 rye grass organic
30 rye grass organic
^30 rye grass organic
30 Kentucky fescue grass organic
30 Kentucky fescue grass organic
30 rye grass sandy
30 rye grass sandy
30 rye grass sandy
30 Kentucky fescue grass sandy
30 Kentucky fescue grass sandy
30 Kentucky fescue grass sandy
30 rye grass clay
30 rye grass clay
30 Kentucky fescue grass clay
43 rye grass organic
43 Kentucky fescue grass organic
43 Kentucky fescue grass organic
70 rye grass organic
70 rye + weed contaminant organic
70 lettuce organic
70 weed + contaminant organic
70 Kentucky fescue grass organic
70 Kentucky fescue grass organic
70 rye grass sandy
70 rye grass sandy
70 weed contaminant sandy
70 weed contaminant sandy
70 rye grass clay
70 Kentucky fescue grass clay
70 weed contaminant clay
103 rye grass organic
103 rye grass organic
103 lettuce organic
103 lettuce organic
103 lettuce organic
103 Kentucky fescue grass organic
103 weed contaminant organic
103 weed contaminant organic
103 rye grass sandy
103 rye grass sandy
103 rye grass sandy
103 Kentucky fescue grass sandy
103 rye grass clay
103 rye grass clay
103 rye grass clay
103 Kentucky fescue grass clay
103 weed contaminant clay
PH
chelated
control
pH
control
pH
chelated
control
PH
chelated
control
pH
pH
control
control
pH
chelated
control
chelated
chelated
control
chelated
control
pH
pH
chelated
che lated
control
pH
control
chelated
control
PH
chelated
PH
control
chelated
control
pH
chelated
control
control
pH
chelated
pH
control
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
+ pH
119
135
10.0
13
40
90
85
14
129
115
<1
35
88
<1
5
143
33
10
15
18
6
18
15
9
15
38
145
7.9
55
6
23
<1
8
8
5
4
8
<1
15
15
2.5
17
15
28
55
<1
190
-------
Day
30
30
30
30
30
30
30
30
30
30
43
A3
A3
A3
70
70
70
70
70
70
70
70
70
70
70
70
70
10A
10A
10A
104
10A
10A
10A
10A
10A
10A
10A
10A
10A
10A
TABLE 57. CADMIUM LEVELS IN PLANTS AND SOIL TREATMENT
Cadmium Levels;
Plant Type
Soil Type
Soil Treatment
ppm Dry Weig
rye grass
organic
control
9.5
rye grass
organic
PH
. 1A3
rye grass
organic
chelated
+
pH
321
Kentucky fescue grass
organic
control
<.5
Kentucky fescue grass
organic
chelated
+
pH
273
rye grass
sandy
control
2.5
rye grass
sandy
PH
20A
rye grass
sandy
chelated
+
pH
900
Kentucky fescue grass
sandy
PH
8A
Kentucky fescue grass
sandy
chelated
+
PH
A88
rye grass
organic
control
2 1
Kentucky fescue grass
organic
control
<•5
Kentucky fescue grass
organic
PH
12.8
Kentucky fescue grass
sandy
PH
1A6
rye grass
organic
control
<.5
rye grass
organic
PH
A1
weed contaminant
organic
control
A 3
weed contaminant
organic
chelated
+
pH
75
rye grass
sandy
pH
125
rye grass
sandy
chelated
+
PH
120
lettuce
sandy
PH
350
weed contaminant
sandy
PH
22
weed contaminant
sandy
chelated
+
PH
75
rye grass
clay
PH
56
rye grass
c lay
chelated
+
PH
188
weed contaminant
c lay
control
< .5
weed contaminant
clay
pH
7A
rye grass
organic
control
2
rye grass
organic
PH
20
rye grass
organic
chelated
+
PH
39
lettuce
organic
PH
AO
lettuce
organic
chelated
+
PH
123
swiss chard
organic
chelated
+
PH
25
Kentucky fescue grass
organic
control
1
weed contaminant
organic
control
< 5
weed contaminant
organic
PH
9.8
weed contaminant
organic
chelated
+
PH
37
weed contaminant
organic
chelated
+
pH
AA
rye grass
sandy
control
< .5
rye grass
sandy
chelated
+
pH
79
swiss chard
sandy
chelated
+
Ph
37
(continued)
191
-------
TABLE 57. (CONTINUED)
Cadmium Levels,
Day
Plant Type
Soil Type
Soil Treatment
ppm Dry Weight
104
Kentucky fescue grass
sandy
control
< .5
104
Kentucky fescue grass
sandy
chelated + pH
38
104
weed contaminant
sandy
control
1.3
104
weed contaminant
sandy
chelated + pH
53
104
rye grass
clay
control
1 7
104
rye grass
clay
pH
49
104
weed contaminant
clay
control
1.0
104
weed contaminant
clay
pH
45
104
weed contaminant
clay
chelated + pH
47
192
-------
Plant samplings after day 30 usually had lead levels less than 100 ppm. Two
exceptions were the rye grass on day 70 from the chelated clay soil which had lead
levels of 145 ppm. Also the Kentucky fescue grass on day 43 from the acidic
organic soil had lead levels of 143 ppm. The lettuce did not accumulate lead to
levels greater than 10 ppm.
The data on the uptake of cadmium by plants are presented in Table 57. Three
collections of the grasses and one or two collections of the lettuce or chard were
conducted during the study.
The highest cadmium uptake was observed on day 30 in the chambers receiving
the chelating agent disodium EDTA. The rye grass had cadmium levels from the
organic and sandy soils of 321 and 900 ppm. The Kentucky fescue grass had cadmium
levels from the organic and sandy soils of 273 and 486 ppm, respectively. The
lettuce, sampled on days 70 and 104, had cadmium levels of 350 and 123 ppm,
respectively, from the sandy and organic soil chambers. The swiss chard sampled
day 104 had levels of 37 ppm in the chelated sandy soil chamber.
Discussion of Results
Overall, the plants grown in the chelated soils had higher metal levels.
Chelating agents increase the plant uptake of metals by solubilizing the metals
and increasing their diffusion to root surfaces (Wallace e£ al_. , 1978). The
disodium EDTA was added to the soil only once in the early part of the experiment
This chemical is biodegradable and was probably removed from the soil. It
appears that repeated applications of EDTA or other chelating agents would make
the metals more available to the plants on a continuous basis and thus increase
the removal of the metals from the soil For cadmium, EDTA significantly
increased the uptake of the metal by the vegetation. The results were not as
dramatic for lead.
The reduction of cadmium concentrations in the chelated soils during the
experiment was due to the uptake of cadmium by the plants and leaching of the
metal from the soil. The cadmium concentrations in the chelated sandy soil
chamber decreased by about 50%. The grasses sampled from the chamber during the
first 30 days accounted for 1-2% of the metal loss. If the grass had been planted
in the entire chamber and complete harvesting had been conducted, the amount of
metal removed would have been greater. However, at least several harvests would
need to be conducted before significant losses of cadmium from the soil would
occur
193
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SECTION 9
EVALUATION OF THE LAND RESTORATION TECHNIQUES
The results of the laboratory studies on the four land restoration
techniques were evaluated for their applicability to real-life spill situations
by the following criteria-
applicability to and effectiveness for a wide variety
of spilled hazardous materials, soil conditions and
weather conditions
degree of acceleration of recovery rates
cost of treatment
The enhancement of iji situ microbial degradation by indigenous micro-
organisms surviving the spill was studied in Technique I. To enhance the
microbial degradation, essential nutrients are added to the soil with or without
plowing for aeration. This technique offers a low cost method for accelerating
the restoration of spill damaged lands. However, it is only effective for water
soluble, low microbial toxicity and easily biodegradable chemicals such as
ammonium acetate. The microbial population can not adapt rapidly enough to
degrade volatile compounds of low water solubility such as monochlorobenzene.
Water insoluble compounds, e.g., Ethion, also can not be degraded to any extent
by thi9 method. The chemical must come in contact with the cell to be degraded
(Stanier, et al. , 1963). The technique is applicable to a wide variety of soil
conditions when the proper nutrients are supplied. Weather conditions are a major
factor in the effectiveness of this land restoration technique. Since microbial
degradation proceeds most rapidly under warm, moist conditions, Technique I
would be of little value in cold (<0°C) weather.
In Technique II, a mixed culture of microorganisms obtained from primary
sewage effluent was applied to the spill-damaged land with and without additional
nutrients. This technique is a low-cost, effective method of accelerating the
removal of water soluble, biodegradable organics from the soil. The data
obtained during the experimental phase of the programs indicate that this method
can accelerate the removal of the spilled chemical from most soil types. In
general, organic and sandy soils yield the highest rate of removal. Drawbacks to
Technique II are cold weather and the fact that the chemical must be water soluble
or made water soluble by an acid/base reaction.
Technique III is a promising approach for the future even though only minor
success was obtained in this program. This approach applies microbial
194
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degradation methods to environmentally persistent compounds such as the poly-
chlorinated organics and organic nitro compounds. The method used in the
experimental phase of this program was to adapt a pure or mixed culture of
microbes to use the chemical as the sole carbon source through a series of
subculturing techniques. This procedure can be taken one step further. Instead
of an adaptation/mutation procedure, the organisms can be genetically engineered
to contain the proper enzyme systems to degrade particular chemicals. Both the
adapted/mutant and genetic engineering approaches require a stock pile of
microorganisms for use in a spill situation. In addition, significantly more
research is needed in this area to develop the organisms for degrading the
chlorinated organics. The limited water solubility of these compounds is still
a problem. The organisms must also possess the ability to concentrate these
lipid soluble-water insoluble chemicals so that sufficient quantities are
available to them for degradation.
To summarize, Technique III, has four drawbacks, 1) more research is needed
to develop the microorganisms, 2) the cost of spill clean-up is higher than for
Techniques I or II, 3) the technique will not work in temperatures consistently
below 0°C, and 4) soil nutrient conditions must be maintained in the proper
balance. However, it is still less expensive than removal of the soil or doing
nothing and permitting the chemical to remain in the soil.
The selective absorption of chemicals by harvestable plants (Technique IV)
is useful primarily for metals, however, it is also useful for removing some
organics from the soils, e.g., Ethion. The soil conditions must be optimized to
favor uptake of the chemical by the plants. In the case of metals, acidic soils
and chelating agents greatly improve the uptake. The method can accelerate the
removal of hazardous chemicals from the soil However, it has some limitations;
1) the plants cannot grow in the presence of very high concentrations of certain
metals and chemicals, 2) the technique is only effective in removing the chemical
during the growing season, 3) the soil must be continuously monitored and treated
to optimize plant uptake of the chemical, 4) the vegetation must be harvested on
a regular basis and either landfilled in a secure landfill or otherwise properly
disposed of and 5) animals must not be allowed to forage on the vegetation.
All these in situ techniques are slow (they will not restore the land in a
few days or weeks), however, they are less expensive than most of the methods that
have been applied to land restoration in the past. For near future applica-
bility, Techniques II and IV have the greatest potential. Technique I has very
limited use and Technique III is still in the early research stages.
195
-------
SECTION 10
FIELD DEMONSTRATION TEST DESIGN
For a land restoration method to be of value, it must be viable under real-
life spill and environmental conditions. This section presents a test plan for
demonstration of two land restoration techniques on three chemicals under actual
environmental conditions - microbial degradation and vegetative uptake of
metals. The choice of techniques to be evaluated in the field demonstration was
based on the results of the laboratory studies. The test plan, as presented is
based on simulated spills of the hazardous materials. However, an actual spill
could also be evaluated, if desired The test plan is composed of four tasks.
The experimental procedure to be used in the tasks are discussed in the following
sections.
SITE SELECTION AND PRETEST PREPARATION - TASK I
Task I - Pretest Preparation
During Task I, the sites for the simulated spills to be conducted in Tasks
II, III and IV will be selected These spill sites will be located at ARC's
Gainesville, Virginia facility Two sites, representing a high textured (sandy-
sandy loam) soil and a medium to heavy textured (loam-clay loam) soil, will be
chosen to evaluate soil effects on restoration techniques used to decontaminate
land The following criteria will be used in choosing spill sites:
sufficient land area to accomodate plots for
Tasks II, III and IV
relatively uniform slope (less than 2% slope)
homogeneity of soil type and texture
minimum possibility of hazardous materials being
transported from the plot area by water movement
through the soil either horizontally or through
percolation to the water table
preferably soil pH in the range of 6 0 to 7 0
moderately high soil fertility levels
Site selection will be based on information in the soil survey manual for Prince
William County and on-site inspection. If suitable sites are not available,
soils may be altered (i e , lime and/or fertilizer addition) or an alternative
196
-------
area may be located. In addition, if the potential exists for the chemicals to
leach into ground water, a plastic liner will be used underneath the treated
soil.
Separate plots for Tasks II, III and IV will be constructed at each soil
type-site. As it is not known if the soil type will vary in one or two dimensions,
the plot design will be set up as a Latin square. This design will allow for
blocking in either or both directions across plots as needed to remove variation
due to soil If the soil does not vary appreciably in the plots, the results may
be analyzed as a completely random experiment.
The plot design is illustrated in Figure 56. Three treatments (unamended,
amended with hazardous chemical(s), and amended with hazardous chemicals and
then receiving a reclamation treatment) with three replications are included in
each set of plots. For each plot, a 2 1x2.1 m (7x7 foot) area will be sectioned
off with either plastic or aluminum edging. A 1.5x1.5 m (5x5 foot) area in each
plot will receive the appropriate treatment The borders around the treated area
will be grassed, and along with the edging will serve to prevent cross
contamination of plots by horizontal movement of soil and water flow.
Soil parameters to be measured prior to initiation of Tasks II through IV
are.
CEC - total nitrogen
soil pH - potassium
soil bacteria - phosphorus
soil fungi - soil texture
soil actinomycetes - soil metal levels
Techniques for these determinations will be as described in Methods of Soil
Analysis, American Society of Agronomy Monograph No 9 (1965). This task will
require one month to complete.
LAND RESTORATION AFTER A FORMALDEHYDE SPILL - TASK II
The microbial degradation of formaldehyde in the soil will be evaluated in
this task. Plots in the two sites chosen in Task I will receive the following
treatments.
untreated
formaldehyde addition
formaldehyde addition followed by addition of
mixed microbial culture
197
-------
2.13 M
•SUFFER
STRIP
•PLOT
1.51
-6.40 METERS.
Figure 56. Test Plot Design.
198
-------
Formaldehyde at the rate of 0.11 g/cm2 (6 liters/plot) will be applied
uniformly on the appropriate plots. After 48 hours, 11 5 liters of a mixed
microbial culture, isolated from primary sewage effluent, will be applied to
three of the plots containing the formaldehyde. The microorganisms will be grown
up in a nutrient salts solution containing 5000 ppm formaldehyde. The organisms
which can utilize formaldehyde will be selected.
Plots will be sampled at 24 and 48 hours, then every third day for three
weeks, and then weekly for the next 7 weeks. Four 2.5 cm core samples will be
removed from each plot. The cores will be divided into 0-15.24 cm, 15.24-30 48
cm, 30.48-60.95 cm, and 60.95-91.44 cm segments. Pooled sub-samples from each
plot will be used for chemical and microbial analyses. Samples will be stored in
polyethylene bags and returned to the laboratory within two hours for immediate
formaldehyde and microbiological analyses.
Formaldehyde will be extracted from the moist soil by shaking approximately
25 grams of soil with 50 ml of distilled water The mixture will be allowed to
stand for 1 hour, then decanted, and the supernatent centrifuged at 3200 rpm
This procedure will be repeated and the combined supernatants will then be put
into GC autosampler vials. The samples will be quantified using a Varian 3700 GC
with autosampler and flame ionization detector under the following conditions.
injection port temperature' 290°C
oven temperature: 135°C
carrier gas: N2 at a flow rate of 30 ml/min
Column: Porapak T
The peak areas will be integrated with a Varian CDS 111. The results will be
compared to a standard curve obtained with known concentrations of formaldehyde
in water
A one gram sample of moist soil will be serially diluted with sterile water
and plated for total bacteria, fungi and actinomycete determinations according
to methods described in Methods of Soil Analysis, ASA Monograph No. 9 (1966) A
third subsample of the soil will be used to determine soil moisture (dried 24
hours at 106°C). The remaining soil will be air dried and pH determined on a 1.1
soil.water slurry using a pH meter and combination glass-calomel electrode.
The following parameters will be evaluated using analysis of variance
(AN0VA):
formaldehyde content
soil actinomycetes
soil bacteria
soil pH
199
-------
soil fungi
The degree of soil variability in the plot areas is not presently known If soil
type is found to vary in two directions, a latin square model may be used to test
for treatment differences within each sampling. However, no valid statistical
design will allow for testing differences becween sampling times. The ANOVA
table for the latin square design would be as shown in Table 58.
It is not expected that any interactions between Rows, Columns, and
Treatments will exist. Thus, it will be assumed that all interactions are not
significant. If for most sampling items, variation in either Sows or Columns is
not significant, it will be assumed that blocking in two directions is not needed
and all data will be analyzed as a factorial experiment with blocking. The ANOVA
table for this design would be as shown In Table 59.
If blocking does not significantly reduce the error term, the data will be
analyzed in a two-way analysis of variance Table 60 Illustrates how data is
handled by this model.
Ideally the plot sites will be selected so as to reduce soil variability and
thus eliminate the need for blocking It is expected that the completely random
two-way classification design will be used.
Prior to calculations for the analysis of variance, the data will be
analyzed for homogeneity of variance using the Burr-Foster Q test (Anderson and
McLean, 1974). It is probable that a log transformation will be necessary to
correct for non-homogeneity of variance for several factors, notably the
microbiological determinations
TABLE 58. ANOVA: LATIN SQUARE DESIGN
Source of
Variation
Degrees of
Freedom
Sl'Cl of
Squares
Mean
Square
F
Ratio
Rows (r)
2
SSr
SSr/2=MSr
MSr/s2
Column (c)
2
SSC
ssc/2=msc
MSc/s2
Treatments (t)
2
SSt
SSt/2"MSc
MS;/s2
Error
2
SSe
SSe/!=s2
Total
8
SScotal
200
-------
TABLE 59. ANOVA: FACTORIAL EXPERIMENT WITH BLOCKING
Source of
Degrees of
Sum of
Mean
F
Variation
Freedom
Squares
Square
Ratio
Blocks (b) (either
row or columns)
2
SSb
SS./2-MS.
d b
MSb/s2
Treatments (t)
2
SSt
SSt/2=MSt
MSt/s2
Sampling Times (s)
15
SS
s
SS /5=MS
s s
MSs/s2
Interaction of TXS
30
SS.
txs
SSt*s/3°-
^txs
MStxs/s2
Error
94
SS
e
SS /94=s2
e
Total
143
SS
total
TABLE 60. ANOVA:
TWO-WAY ANALYSIS
Source of
Degrees of
Sum of
Mean
F
Variation
Freedom
Squares
Square
Ratio
Treatment (t)
2
SSC
SSC/2=MSC
MSc/s2
Sampling time (
s) 15
SSs
SSs/15"MSs
MSs/s2
Interaction of
TXS 30
sstxs
SSCxs/30°
MSt.X3/s2
MStxs
Error
96
SSe
SSe/96=s2
Total
143
sstotal
201
-------
All statistical testing will be performed at the 52 level of probability
Where significance is indicated by the ANOVA, the Student-Newman-Keuls multiple
range test will be employed to compare means The means of parameters analyzed
in log form will be presented as geometric means. All other means will be
presented as arithmetic means. Task II will take three months to complete
LAND RESTORATION AFTER AN ANILINE SPILL - TASK III
An aniline spill will be simulated as described for the formaldehyde spill
in Task II The treatments will be as described in Task II except aniline will
be applied at 0.27 g/cm2 (6 liters/plot) and the reclamation treatment will
consist of adding 11 5 liters of adapted sewage effluent previously incubated in
the presence of 5000 ppm aniline, with additions of yeast extract and nutrient
salts to promote microbial growth.
The plots will be sampled at 24 and 48 hours, and then weekly for the next
15 weeks Sampling procedures will be as stated in the Task II experimental
description.
Aniline will be determined in the soil by solvent extraction and gas
chromatograph quantification. Two grams of moist soil will be shaken with 0.5 ml
of 24Z solution NaOH in methanol and 4 0 ml of 50*50 methanol-methylene chloride
mixture This mixture will then be centnfuged and decanted. An additional 4 0
ml of methylene chloride will be added to the soil, shaken, centnfuged and
decanted. The combined liquid will be shaken with 6.0 ml of distilled water and
then centnfuged. A subsample of the methylene chloride layer will be used for
gas chromatographic analysis. The gas chromatograph will be a Varian 3700 GC with
a flame ionization detector operated under the following conditions.
- injection port temperature 300°C
oven temperatures: 140"c for 4 minutes; increased
temperature 20°C/minute for 2
minutes, 180°C for 3 minutes
detector temperature. 300°C
carrier gas N2 at a flow rate of 30 cc/min
column 1 82M x 0.2 mm ID 10Z Carbowax 20 m/25! KOH on
Chromosorb WAW
The peak areas will be integrated with a Varian CDS 111. The results will be
compared to a standard curve obtained with known concentrations of aniline in
water
Microbiological determinations, pH and percent moisture will also be
determined as described in Task II The statistical treatment of the data will
be as stated for Task II
202
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LAND RESTORATION AFTER A SPILL OF CADMIUM NITRATE - TASK IV
The feasibility of renovating Cd contaminated soil by vegetative uptake and
removal will be examined in Task IV Plots on both soil types chosen in Task I
will receive the following treatments
untreated
Cd addition
Cd addition followed by treatment with EDTA
Cadmium as Cd(N03>2 at the rate of 1 6 x 10~2 g/cm2 (328 g/plot) will be
applied uniformly in a dilute solution on the appropriate plots After a minimum
of 30 days, ethylenediaminetetraacetic acid (EDTA) will be applied to three of
the Cd treated plots (0.25 ml of 0 1M NaEDTA/cm2 or 5.8 liters of 0 1M
NaEDTA/plot)
Each plot will be divided into three areas for seeding rye grain, swiss
chard and perennial rye grass The EDTA application will be timed to roughly
precede seeding by one week.
The rye gram and rye grass will be harvested at maturity Grain and
vegetative tissue will be analyzed separately for the total Cd concent Swiss
chard will be harvested 40 days after emergence for total Cd determination Dry
matter of the vegetative growth and grain yield will be measured for all crops
Soil samples will be collected at planting and harvesting times Four 2.5
cm core samples will be removed from the soil supporting each crop in every plot
The cores will be separated into 0-15 24 cm and 15 24-30 48 cm segments and total
Cd extracted and quantified. Soil pH will be measured as previously described
for Task II.
Cadmium determinations for both plant and soil samples are described by
Isaac and Kerber (1971) The methods described as Wet Digestion and Acid
Dissolution will be used for tissue and soil analyses, respectively. The
statistical treatment of the data will be as stated in Task II description.
203
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SECTION 11
OPERATING PROCEDURES FOR RESTORATION OF SPILL-DAMAGED LANDS
The purpose of this section of the report is to provide a guide to aid the
on-site spill response coordinator in selecting an appropriate restoration
technique for a land area damaged by a spill of a hazardous chemical, sludge,
paint or petrochemical wastes. The restoration techniques are to be applied
after the clean-up of the major portion of the spilled material The goals of any
land restoration technique are to restore the land to its original condition (or
better) and prevent movement of toxic chemicals in the environment. The
hazardous chemicals considered in this guide were taken from the hazardous
substances list published in the Federal Register, Vol. 43 (49), p 1047-10474.
The chemicals in this list have been compiled as hazardous substances for spills
in water. Many of these chemicals are not a major problem when spilled on land
except under adverse weather conditions For example, the ammonium salts which
are highly toxic to fish when spilled in waterways, can be used as a nutrient
source by plants. In general, non-water soluble solids and many water soluble
solids can be sufficiently removed from the land surface during the initial
response. Therefore, they do not require extensive land restoration methods.
Applicable land restoration techniques for each of these hazardous
materials have been selected based on the known physical, chemical and biological
properties of the compound. A detailed search of the literature for all the
properties of each chemical was beyond the scope of work. Therefore, the
information on the properties of 271 hazardous chemicals were compiled from the
information available in reference sources such as the CHRIS list and OHM-TADS.
Where sufficient information on a specific chemical was unavailable, scientific
judgement was used to predict its fate in the soil environment The data for the
271 chemicals are presented in Table 61.
Each chemical in the table was classified into four major categories
according
to its
expected fate in the soil environment:
1)
NP:
non-persistent organics and inorganic salts
2)
EP:
environmentally persistent organics
3)
TM.
inorganic and metal organic compounds
containing toxic metals
4) TA. inorganic compounds containing toxic anions
The non-persistent category includes biodegradable organic compounds such as
acetic acid, biouseable inorganic salts, e g., ammonium sulfate, and volatile,
204
-------
TABLE 61. HAZARDOUS CHEMICAL CLASSIFICATION AND APPLICABLE RESTORATION TECHNIQUES
Common Name
O
Ln
75070
64197
108247
75863
506967
79367
L07028
L07131
309002
107X86
107051
10043013
7664417
631618
1863634
1066337
Acetaldehydc
Acetic acid
Acetic anhydride
Acetone cyanohydrin
Acetyl bromide
Acetyl chloride
Acrolein
Acrylonitrile
Aldrin
Allyl alcohol
Allyl chloride
Aluminum sulfate
Ammonia
Ammonium acetate
Ammonium benzoate
Ammonium bicarbonate
Synonyms
Major Environmental
Classification
Environmental
Properties
EthanaL, ethyl aldehyde,
acetic aldehyde
CLocial acetic acid, vinegar
ac Id
Acetic oxide, acetyl oxide
2-methyllactonitrile, alplwi-
hydroxy Isobutyronitrile
2-propenol, acrylic alde-
hyde, ocrylaIdehyde, acralde-
hyde
Cyanoethylene, Fumigrain,
Ventox, propenet«itnte, vinyl
cyanide
'Octalene, IHIDN
2-propen-l-ol, l-propenol-3,
vinyl carbinol
NP
NP
NP
NP
EP
NP
3-chloropropcnc, 3-chloropro- NP
pylene, Chlorallylene
Alum
Acetic acid ammonium salt
Acid ammonium carbonate,
ammonium hydrogen carbonate
EP
NP
NP
NP
NP
8 ,b, r
s »b, r
s, r ,b
s, r ,b
s,r,b,u
8,r,b,u
s,b
s,r,b
i 11(p),r(p)
8 , b
s,r(slovly),b
s,n
s,r,u
8 ,U
s ,u ,b
s,u
Applicable Land
Restoration Technlque(s)
III,II,VIII
III,II,VIII
II,VIII
III,II,VIII
III,II,VIII
II,VIII
V, (VII),(II)
II
II
III,VIII
II,VIII
II,VIII
I,VIII
(continued)
-------
TABLE 61 (CONTINUED)
CAS No
O
Common Name
7789095
1341497
10192300
1111780
506876
12125029
7788989
3012655
13826830
12125018
1336216
6009707
5972736
14258492
16919190
7773060
12135761
10196040
10192300
Anmonium bichromate
Ammonium bifluorlde
Ammonium bisulfite
Ammonium carbamate
Ammonium carbonate
Amnion turn chloride
Ammonium chromatc
Synonyms
Major Environmental
Classification
Acid ammonium fluoride,
ammonium hydrogen fluoride
Ammonium amlnoformate
Ammonium muriate, sal
ammoniac, salmlac, Amchlor
Ammonium citrate dibasic Diammonium citrate, citric
acid, dlammonlum salt
Ammonium fluoroboratc,
ammonium borofluorlde
Neutral aoimonium fluoride
Ammonium fluoboratc
Ammonium fluoride
Ammonium hydroxide
Ammonium oxalate
Ammonium sLlicofluoride Ammonium fluoslllcatc
Ammonium sulfamate
Ammonium sulfide
Ammonium sulfite
Animate, AHS. ammonium amido-
sulfate
TM
TA
NP
NP
EP
NP
EP
TA
NP
NP
EP
NP
EP
NP
~ Environmen t al
Properties
B,p
6,U
8,U
8,b
S.p
s,b
s.i.n
s,r,u
s,b
a,u,n
8,U
s,n
s,u
"Applicable Land
Restoration Technlque(s)
V.IV.VI
VIH
II,VIII
II.VIII
IX,VIII
II,VIII
1V,V,VI
II,VIII
VIII
VIII
III,VIII
II,VIII
VIII
VIII
VIII
VIII
(continued)
-------
TABLE 61 (CONTINUED)
CAS No
316*292
14107438
1762954
7783188
628637
62533
7*47189
28300745
77B9619
10D25919
7782564
1303328
1303328
778431
1327533
Coppon Name
Annuonturn tartrate
Ammonium thiocyanate
Ammonium thloaulfate
Amy I acetate
Aniline
Ant loony pent«chlorida
Antimony potassium
tartrate
Antimony trlbromido
Antimony trichloride
Antimony trifluorlde
Antimony tnoxide
Arsenic disulfide
Arsenic trichioride
Arsenic tnoxide
Synonym3
Major Environmental
Classification
Environmental
Properties
Tartaric acid ammonium salt
Ammonium rhodanlde, ammonium
sulfocynnabe, ammonium eulfo-
cyanlde
Ammonium hyposulflte
Amylacetlc ester
Pear oil
Banana oil
Aniline oil, phenylamlne,
amlnobenzene, atnlnophen,
kyanol
Tartar emetic, tartrate^
antimony, tartarl2ed anti-
mony, potassium antimonyl-
tartratc
Butter of antimony
Antimony fluoride
Diantimony tnoxide, flowers
of antimony
Red arsenic sulfide
Arsenic chloride, arsenious
chloride, arsenious chlor-
ide, butter of arsenic
Arsenious acid, arsenious
oxide, white arsenic
NP
NP
TH
TM
TH
TM
TM
TM
TM
TM
8 ,u
a ,b
s,r ,b
s,r,p
s,ulP
s.r.p
s, r, p
s,r,p
i.P
r»P
s,p
Applicable Land
Restoration Technique(s)
II,VIII
II.V1II
II.VIII
II
II,VIII
V, III,IV
V,{IV)
V,(IV)
V,
-------
TABLE 61 (CONTINUED)
o
00
Common Name
1303339 Arsenic trlsulflde
542621 Barium cyanide
71432 Bcnzen
65850 Benzole acid
1004 70 Bcnzonltrlie
98684 Benzoyl chloride
100447 Benzyl chloride
7787475 Beryllium chloride
7787497 Beryllium fluoride
7787555 Beryllium nitrate
13597994
123064 Butyl acetate
Synonyms
Arsenlous sulfide, yellow
arsenic sulfide
Cyclohexatricne, benzol
BcnscnccarboxyLlc acid,
phenylformlc acid, dracyllc
acid
Phenyl cyanide, cyanobenzene NP
Benzenecarbonyl chloride
NP
TH
TM
TM
Acetic acid butyl ester
Major Environmental
Class!fleation
TM
NP
NP
Environmental
Properties
i.P
e,p
i ,v ,b
s,b
s.r.b
a,r,b
i.v.r.b
a.P
s.p
S.P
s,v,r,b
109739
Butylomlne
1-amlnobutane
f»,r,b
107926
543908
7789426
10108642
Butyric acid
Cadmium acetate
Cadmium bromide
Cadmium chloride
Butanolc ocid, ethyl-
acetic acid
NP
TM
TM
s,b
s.p
s,P
Applicable Land
Restoration Technique(e)
V.(IV)
V,(IV)
I
II
II,VI
III,11
II
V,(IV)
V,(IV)
V,(IV)
II
III,II,VIII
III,II,VIII
V.IV
V,IV
(continued)
-------
TABLE 61 (CONTINUED)
CAS No
Common Name
K>
O
7778441
52740166
75207
13765190
592018
26264062
1305 620
7778534
1305788
133062
63252
75150
57749
75003
108907
67663
2921882
7790945
1066304
Calcium arsenate
Calcium arscnltc
Calcium carbide
Calcium chromate
Calcium cyanide
Calcium dodecylbenzene-
sulfonate
Calcium hydroxide
Calcium hypochlorite
Calcium oxide
Captan
Corbaryl
Carbon disulfide
Chlordane
Chlorine
Chlorobenzcne
Chloroform
Chlorpynfoa
Chlorosulfonlc acid
Chromic acetate
Synonyms
Major Environmental
Classification
Trlcalclum orthoarsenate
Carbide, acetylenogcn
Calcium chrome yellow,
geblin, yellow ultramarine
Lime, hydraced slaked lime,
calcium hydrate
Lime, quicklime
Orthocide-406, SR-406,
Vancide-89
Carbon bisulfide, dithlo-
carbonic anhydride
Toxlchlor, chlorodan
Monochlorobenzen, benzen
chloride
Trlchloromethane
Dursban
Sulfuric chlorohydrla
TM
TM
NP
TA
TA
NP
NP
NP
NP
NP
NP
EP
NP
NP
NP
NP
NP
TO
Environmental
Properties
i.P
a, r,u
s.r.p
s,b,u
a,b,u
s, r ,u
8,r,u
s.r.b
a, r,b
a, r ,u
i.r.P
s.r.u
1, v,b
l,v,r,b
s,r,b
s, r,u
s.r.p
Applicable Land
Restoration Technlque(s)
V.1V
V,IV
III
I
III,VIII
I
III
III
III
III,II
II
I
V.VII
III,VIII
II
I
II
III,VIII
V,IV
(continued)
-------
TABLE 61 (CONTINUED)
Major Environmental Environmental Applicable Land
ho
I—*
O
CAS No
Common Name
Synonyms
Classlflcation
Propertles
Restoration
11115745
Chromic acid
Chromic anhydride, chromiua
trloxlde
TH
a,r ,p
V,IV
1010133a
Chroolc sulfate
TM
s,r,p
V,IV
10049055
Chromous chloride
TH
s,r,p
V,(IV)
7789437
Cobaltous bromide
Cobalt bromide
TM
s,r,p
V.(IV)
544183
Cobaltous formate
Cobalt formate
TM
a,r,p
V,(IV)
14017415
Cobaltous sulfamate
Cobalt sulfamate
TH
s,r,p
v,(iv)
56724
Coumaphos
Co-Ral
KP
i,r ,b
II
1319773
Crcsol
Cresyllc acid
Hydroxytolucne
NP
s,b
III,II,VIII
142712
Cuprlc acetate
Copper acetate, crys-
talized verdigris
TM
s,r,p
IV
12002038
Cuprlc acetoarsenltc
Copper acetoarsemte,
copper acetate arsenite,
Paris green
TM
i.P
IV
7447394
Cupric chloride
Copper chloride
TM
s.r.p
IV
3251238
Cuprlc nitrate
Copper nitrate
TM
s.r.p
IV
5893663
Cupric oxalate
Copper oxalate
TM
s.r.p
IV
7758987
Cuprlc sulfate
Copper sulfate
TM
s.r.p
IV
1036B297
Cupric sulfate,
ammoniated
Ammoniated copper sulfate
TM
s.r.p
IV
815827
Cuprlc tartrate
Copper tartrate
TM
s.r.p
IV
506774
Cyanogen chloride
NP
s.v.r
III,VIII
110827
Cyclohexane
Mexahydrobenzene, hexa-
NP
l.v.r.b
I
methylene, hexanaphthene
(continued)
-------
TABLE 61 (CONTINUED)
CAS No. Common Name
94757
94X11
94791
94804
1320189
1928387
1928616
1929733
2971382
25168267
53467111
50293
333415
2,4-D acid
2,4-D ester
DDT
Dlaslnon
1918009 Dlcamba
1194656 DUtilobenil
117606 Dichlone
75990 2,2-Dichloropropionic
acid
62737 Dlchlorvos
60571 Dleldrin
109897 Diethylaralne
124403 Dlmcchylamlne
25154545 Dlnlirobenzene (mixed)
Synonyms
Major Environmental Environmental
Classification Properties
2,4-dichlorophcnoxyacetlc
acid
2,4-dichlorophenoxyacetic
acid ester
p,p-DDT bp
Dlpofcne, Diazitol, Basudin HP
Spectraclde
2-oethoxy-? ,6-dlchlorobentolc HP
ac id
2,6-dichlorobenzonitrlie, NP
2,6-DBN
Phygon, dlchloronaphchoquinone EP
Dalapon EP
2,2-dichlorovlnyl dimethyl NP
phosphate, Vapona
Alvlt EP
NP
NP
Dlnltrobcnzol EP
s.b
l,b
l,b,r
8,b
1 ,b
l.P
s ,n
s,r,b
i.P
S tb
8 fb
s,t,p
Applicable Land
Restoration Technlque(s
II
VII, V
II
II
II
V,VI(VII
V,II,VII
II,III
v,vti
I
I
V.II.VI
(continued)
-------
TABLE 61 (CONTINUED)
Coampn Name
Synonyms
Major Environmental
Claaslflcatlon
Environmental
Properties
51285
(2,4-)
85007
2764729
298046
330541
27176870
115297
72208
563122
100414
107153
60004
1185575
2944 674
55488874
770508 0
7783508
10421484
Dlnltrophenol
Diquat
Dlsulfoton
DLuron
Dodecylbenzenesulfonic
acid
Endosulfan
Endrln
Ethlon
Ethylbenzene
Ethyltnedlamlne
Ethylenediamlnetetra-
dcetlc acid (LDTA)
Ferric annnoniun citrate
Ferric ammonium oxalate
Ferric chloride
Ferric fluoride
Ferric nitrate
Aldlfen
Aquaclde
Dextrone, Reglone, Diquat
dlbroroldc
Dl-syston
DCMU, DHU
Thlodan
Mendrln, Compound 269
Nlalate, ethyl methylene,
phosphorodlthloate
Phenylethane
1, 2-dlanlnoethane
Edetic acid, Havidote,
(ethylenedlnUrilo)-tetra-
ocetic acid
Ammonium ferric citrate
Ansnonlum ferric oxalate
Flores martla, Iron tri-
chloride
Iron nitrate
EP
EP
NP
EP
EP
EP
NP
NP
EP
EP
TA
EP
s,p,b
l.t.p
s,b
l.P
8,p
i ,b ,v
s ,b
s,b
s,b,u,n
s,b,u,n
s,u,n
s,u,n
e,u,n
Applicable Land
Restoration Technique^)
V.1I.VT
V,II,IV
II,VI
V.II
III,II,VIII
V
V,VII
II,VI,IV
III,II,VIII
III,II,VIII
III,IV
111,1V
HI,IV
III,IV
III,IV
(continued)
-------
TABLE 61 (CONTINUED)
Common Name
r-o
10028225 Ferric sulfate
10043093 Ferrous ammonium
sal fate
7758943 Ferrous chloride
7720787 Ferrous sulfate
7782630
50000 Formaldehyde
64186 Formic acid
110178 Fumarlc acid
98011 Furfural
66500 Cuthlon
76448 Hcptachlor
7647010 Hydrochloric acid
7664393 Hydrofluoric acid
74908 Hydrogen cyanide
78795 Isoprene
42504461 Isopropanolarolne
dodccylbenzenesulfonate
Synonyms
Major Environmental Environmental
ClasalfAcatlon Properties
Ferric persulfatc, ferric
sesqulsulfatc, ferric ter-
eulface
Mohr's salt, Iron ammonium
sulfate
Iron chloride, iron dichloride
iron protochloride
Crccn vltrol
Iron vltrol, Iron sulfate.
Iron protosulfate
Methyl aldehyde, nlethanol,
formalin
Hethanotc acid
Trans~butenedlolc acid,
trons-1,2-ethylenedlcarboxyllc
acid, boletlc acid, allomalelc
acid
2-furaldehyde, pyromuclc alde-
hyde
NP
HP
HP
NP
Cuzathlon, azlnphos-methyl
Velsicol-104, Drlnox, Heptagran gp
Hydrogen chloride, muriatic acid
Fluohydrlc acid
Hydrocyanic acid JA
2-methyl-l, 3-butadlene
NP
(continued)
8 ,u ,n
s, b
s,b
9 ,b
s,b
s,r,t,b
i.P
9 ,U
8,U
s,b
l.r.b
8,b
Applicable Land
Reatoratlon Technique(a)
III,IV
III,IV
III,IV
III,IV
II
III,II
III,II
II
111,11
V,VII
III,VIII
III,VIII
III,II,VIII
II
II
-------
TABLE 61 (CONTINUED)
Common none
115322
301042
7784409
7645252
10102484
7758954
13814965
7738462
10101630
7428460
1072351
52652592
7446142
1314870
592870
58899
14307358
121755
110167
108316
Lead acetate
Lead arsenate
Lead chloride
lead fluoborace
Lead fluoride
Lead iodide
Lead atearate
Lead sulfate
Lead sulfide
Lead chiocyanate
Lindane
Lithium chromate
Malathlon
Halelc acid
Maleic anhydride
Synonyms
Major Environmental Environmental Applicable Land
Classification Properties Restoration TechnlqueU',
Dl(p-chlorophenyl)-tr1-
chlorotnethylcarbinol, DTHi
dicofol
Sugar of lead
Lead fluoroborate
Lead difluoride, plum-
bous flourlde
Stearic acid lead salt
Galena
Lead sulfocyanate
Gamma-BHC, gamma-benzene
hexachlorlde
Phospothlon
Cis-butenedlolc acid, cis-1,2-
ethylencdicarboxylic acid,
toxillc acid
EP
TM
TM
TM
TM
TM
TM
TM
TM
TM
TO
EP
TM
NP
NP
2,5-furandione, cis/butcnedioic
anhydride, toxillc anhydride
NP
(continued)
i.p
8,p
l.P
s, r,p
e, r ,p
s*r,p
6 , C , p
s, r, p
i.P
i,P
s.r.p
i.P
e.p
e,r,b
s,b
a, r,b
V.VII
V,IV,III
V,IV,III
V,IV,III
V,IV,III
v,iv,iii
V,IV,III
V,IV(III
V.IV.III
V,IV,III
V.IV.III
V.VII .
V.IV
III,II
III,II,VIII
111,11,VIII
-------
TABLE 61. (CONTINUED)
CAS No.
Common Name
592041
10045940
7783359
592858
7782867
10415755
72435
7493L
80626
298000
7786347
315184
75047
74895
300765
91203
1338245
Mercuric cyanide
Mercuric nitrate
Mercuric sulfate
Mercuric thlocyanate
Mercurous nitrate
Mcthoxychlor
Methyl mercaptan
Methyl methocrylate
Methyl parathion
Muv lnphos
Mcxacarbate
Monoethylamlne
ttonoraethyl amine
Ma led
Naphthalene
Naphthenlc acid
Synonyms
Major Environmental
ClaselfIcatlon
Mercury cyanide
Mercury nitrate, mercury pernltrata
TM
Mercury sulfate, mercury
persulfate
Mercury thlocyanate, mer-
curic sulfocyanate, mer-
curic sulfocyanlde
Mercury protonltrate
DMDT, methoxy-DDT
Methanethlol, mercapto-
methane, methyl sulfhydrate,
thloroethyl alcohol
Mcthacryllc ocld methyl
ester, tnethy l-2-methyl-2-
propenoate
Ni trox-80
PhosdrIn
Zectran
Ethylamlne, amlnoethane
Methylaralne, anInomethane
Dibrom
White tar, tar camphor,
naphthalin
Cyclohexanecarboxylic
acid, hcxahydrobcnzoic acid
HP
HP
HP
HP
HP
HP
HP
HP
HP
Environmental
Propertlea
s • p
.r,p
1 ,b, r
9, V ,U
s ,v,b,r
8,r,b
a,r
s ,b
s,v,b
s,v,b
s,r,b
i, v ,b
a.b
Applicable Land
Restoration Technlque(a)
III,V,IV
V,IV
V,IV
ITI,V,IV
V.IV
II
I
II
III,II
III
II
VIII
VIII
111,11
II
III,II
(continued)
-------
TABLE 61 (CONTINUED)
CAS No
Common Name
15699180 Nickel anmonlutn sulfate
37211055 Nickel chloride
7718549
12054487 Nickel hydroxide
14216752 Nickel nitrate
7786814 Nickel sulfate
7697372 Nitric acid
98953 Hit robenzone
10102440 Nitrogen dioxide
251f>4556 Nltrophenol (mixed)
Synonyms
Major Environmental Environmental
Ammonium nickel sultate
Nickelous chloride
Nickelous hydroxide
Nickelous sulfate
Aqua fortis
Classification
Nitrogen tetraoxlde
Monon11 ropheno1
TM
TM
TM
TM
TM
NP
Nitrobenzol, oil of mlrbane MP
NP
NP
Properties
s,r,p
s.r.P
s,r,p
s.r.p
s,r,p
e»r,u
s,r,b
s,r,u
s,r,b
Applicable Land
Restoration Technlque(a)
V,IV
V(IV
V,IV
V,IV
V.IV
III.VIII
II,VI
III,1V
III,II
30525894 Para formaIdehyde
56382 Parathlon
87865 Pentachlorophcnol
108952 Phenol
75445 Phosgene
7664382 Phosphoric acid
7723140 Phosphorus
Paraform, Fortoagene, Tri-
fonnol, polymerized formal-
dehyde, polyoxymethylene
DNTP, Niran
PCP, Pcnca
Carbolic acid, phenyl
hydroxybensnee, oxybenzene
NT
EP
NP
Dlphosgcne, carbonyl cloride, NP
chlarofortnyl chloride
Orthophosphoric acid EP
Biack phosphorus, red phos- EP
phorus, white phosphorus,
yellow phosphorus
s ,b
s,r,b
s,p
s,b
s,r,n,u
l,r,n,u
II,IV,VI
V,II,VII
III
III
I
III,VI
(coneinued)
-------
TABLE 61 (CONTINUED)
Common Name
10025873 Phosphorus oxychlorlde
1314803 Phosphorus pcntosulfide
7719122 Phosphorus trichloride
1336363 Polychorlnatcd blphenyls
7784410 Potassium arsenate
10124502 Potassium arsenlte
7778S09 Potassium bichromate
7789006 Potassium chrooate
151506 . Potassium cyanide
1310583 Potassium hydroxide
7722647 Potassium permanganate
79094 Propionic acid
123626 Propionic anhydride
121299 Pyrethrlns
121211
91225 Qulnollne
108463 Resorclnol
7446084 Selenium oxide
Synonyms
Major Environmental
Classification
Environmental
Properties
Applicable Land
Restoration Technlque(s)
Phosphoryl chloride, phos-
phorus chloride
Phosphoric sulfide, thlo-
phosphorlc anhydride, phos-
phorus persulflde
Phosphorus chloride
PCB, Aroclor, polychlorlnated
dlphcnyls
Potassium mctaarscnite
Potassium dlchromatc
Potassium hydrate, caustic
potash, potassa
Chameleon mineral
Propanoic acid, methylacetic
acid, cthylformlc acid
Propanoic anhydride, methyl-
acetic anhydride
Pyrethrin I
Pyrethrin II
1-benzazlne, benzo(b)pyridine, NP
leuocolIne.chlnoleine, lcucol
EP
EP
TM
TM
TM
TM
TA
NP
TM
NP
Resorcln, 1,3-benzenedlol,
meta-dl-hydroxybenzene
NP
Selenium dioxide
EP
(continued)
s,r,n,u
i.P
s,r,p
s,r,p
s,r,p
s,r,p
s,b
s,r,u
o,r,p
e,b
s, r ,b
s, r, b
s,r,b
s ,v, r ,b
s.v.r
III
V.VII
Vf IV
V.IV
V.IV
V.IV
II
III
V.IV
III,II,VIII
IIIPII
III,VI,II
III,II
III,II
-------
TABLE 61 (CONTINUED)
CAS No.
Common Noro^
7440235
7631892
7784465
10588019
1333831
7631905
7775113
143319
25155300
7681494
16721805
1310732
7M1529
10022705
124414
7632000
7558794
10039324
10028247
10140655
Sod ium
Sodium Arsenate
Sodium arsenltc
Sodium bichromate
Sodium bifluoride
Sodlum bisulflee
Sodium chromate
Sodium cyanide
Sodium dodecylbenzene-
sulfonate
Sodium fluoride
Sodium hydrosulfi.de
Sodium hydroxide
Sodlua hypochlorite
Sodium methylace
Sodium nitrite
Sodluo phosphate,
dibasic
Synonyms
Major Environmental
Classification
Natrium
Disodlum arsenate
Sodium mctaarsenlte
Sodium dlchromate
Sodium acid sulfite, sodium
hydrogen sulfite
Vllliaumlte
Sodium hydrogen sulfide
Caustic soda, soda lye,
sodium hydrate
Bleach
Sodium tnethoxlde
HP
TM
TM
TM
TA
NP
TM
TA
HP
TA
TA
NP
NP
NP
EP
Environmental
Properties
e,r,u
s,r,p
s,r,p
s.r.p
8 ,U
s.u
s,r,p
s ,b
s, b
svu
a ,u
8 ,U
s.b
8 ,U
e,n
Applicable Land
Restoration Technique(s)
III
V.IV
V.IV
V,IV
I
I
V, IV
II
II
I
I
III
III
IV
III
(continued)
-------
TABLE 61 (CONTINUED)
CAS Mo.
7785844
7601549
10101890
10361894
7758294
10124568
10102188
7782823
7789062
57249
100425
7664939
12771083
93765
2545597
93798
61792072
1928478
25168154
72546
78002
107493
108183
8001352
Common Name
Sodium phosphate,
trlbaslc
Sodium selenltc
Strontium chromdte
Strychnine
Styrene
Sulfuric acid
Sulfur oonochlorlde
2,4,5-T acid
Synonyms
Major Environmental
Classification
Environmental
Propertlea
2,4,5-T ester
Vinylbenzene, phenylethylene,
styrol, styrolene, cinnamene,
clnnamol
Oil of vitriol, oleum
Sulfur chloride
2,4,5-trichlorophenoxy-
acetic acid
2,4,5-trichlorophenoxyl/ace-
tic esters
TDE
Tetraethyl lead
Tetraethyl pyrophosphate TEPP
Toluene
DDD
Lead tetraethyl, TEL
Toluol, methylbenzene,
phenylmethane, Methacide
Toxaphene
Caophechlor
TM
HP
NP
MP
HP
NP
EP
TM
EP
HP
EP
(continued)
8.P
s,r,p
s,b
e,r,b
s, r ,u
6, b, r
1, b, r
1 ,b ,p
l.r.p
e,r,n
a,v,r,b
i.r.p
Applicable Land
Restoration Tcchnlque(a)
III
V,IV
V,IV
II
II
ITI.VIII
III,VIII
III,TI
III,II
II.V
V,IV
III
I
V.VII
-------
TABLE 61 (CONTINUED)
CAS No.
52686
25147622
27323417
121448
75503
541093
10102064
36478769
Common Name
Synonyms
Major Environmental Environmental
Classification Properties
Trlchlorfon
Trlchlorophenol
1314621 Vanadium pentoxide
27774136 Vanadyl suLfate
108054
1330207
1300716
557346
14639975
14639986
52626258
1332076
7699458
3486359
Vinyl acetate
Xylene (mixed)
Xyleneol
Zinc acetate
Zinc ammonium chloride
Zinc borate
Zinc bromide
Zinc carbonate
Dipterex
Dylox
Collunosol, Dovlclde 2 or
2S» Ooal, Phenachlor
Triethanol amine
dodecylbenzenesulfonate
Trlethylamlne
Trlmcthylamlne
Uranyl acetate
Uranyl nitrate
Vanadic anhydride, vanadlc
acid anhydride
Vanadlc sulfate, vanadium
sulfate
Acetic acid ethylene ether
Dimethylbenzene
Xylol
Dimethylphenol, hy-
droxydimethylbenzcne
HP
EP
NP
MP
TM
TM
NP
NP
NP
TM
TM
TM
TM
TM
(continued)
a,r,b
s,p
s,r,b
s,b
s »b
s,r,p
s,r,p
s,r,p
s.p
s ,b
i ,v,b
8, b
8,r,p
s,r,p
s,r,p
8,r,p
s,r,p
Applicable Land
Restoration Technique(e)
III,II
V,II,VH
III,II
III,II,VIII
III,II,VIII
V,IV
V,IV
V.IV
V.IV
II
I
111,11
V.IV
V,1V
V,IV
V.IV
V.IV
-------
TABLE 61 (CONTINUED)
CAS No
Common Name
7646857 Zinc chloride
557211 Zinc cyanide
7783495 Zinc fluoride
557415 Zinc formate
7779864 Zinc hydrosulflte
7779886 Zinc nlcrate
127622 Zinc phenosulfonate
1314B47 Zinc phosphide
Synonyms
Major Environmental
Classification
Butter of zinc
Zinc sulfocarbolate
TM
TM
TM
TM
TM
TM
TM
TM
Environmental
Properties
s«r»P
i.r.p
s.r.p
e,r,p
s.r.p
8, r ,p
a. r ,p
8,r,p
Applicable Land
Restoration Technique(b)
V.IV
III,V,IV
V.IV
V.IV
V.IV
V.IV
V.IV
V,IV
16871719 Zinc sllicofluoride
7733020 Zinc sulfate
13746899 Zirconium nitrate
16923958 Zirconium potabslum
fluorldo
14644612 Zirconium sulfate
10026116 Zirconium tetra-
chloride
Zinc fluorsilicate
White vitriol, zinc vitriol,
white copperas
Disulfatozirconic acid
TM
TM
TM
TM
fM
TM
s.r.p
8,r,p
s.r.p
s.r.p
s,r ,p
s.r.p
V.IV
V.IV
V.IV
V.IV
V.IV
V.IV
-------
non-water soluble organics such as benzene. The environmentally persistent
organics are those compounds which are not readily volatilized from the soil and
those compounds which are not readily volatilized from the soil and are either
not biodegradable or are degraded or transformed to toxic persistent residues.
Examples of compounds in this category are the highly chlorinated organics such
as PCBs, and nitro compounds, such as 2,4-dinitrophenol. The toxic metals
category include to::ic metal salts, e.g , tetraethyl lead, and metal complexes
such as cupric tartrate, and heavy metals containing anions e.g., ammonium
bichromate. Those anions which were considered in the toxic anions category
included fluoride and cyanide salts.
The major environmental properties which determine the fate of the
chemical in the environment and applicable land restoration techniques are then
listed according to the following key.
s: water soluble to the extent of greater than
50 ppm
i. water insoluble less than 50 ppm
b: biodegradable with complete breakdown
and a half-life in soil (actual or predicted) of
less than A months
r: chemically or photochemically reactive
t: biotransformed organic
u: biouseable inorganic
v volatile from soil due to high vapor pressure
codistillation with water, water insolubility
p: persistent toxic residue
n: persistent non-toxic residue
The last column in the table lists potential restoration techniques which
could be applicable to spills of the chemical after the initial spill clean-up.
I
No treatment
II - Biodegradation
III - Neutralization
IV - Vegetative Uptake
V
Physical removal
VI
Chemical reactions
222
-------
VII - Optimization of photodegradation
VIII - Revegetation
ASSESSING THE DAMAGE TO THE LAND
Before any land restoration technique can be employed, the extent of the
damage must first be assessed. Sampling of the spill area with either a soil
corer or trowel. The sampling scheme should outline the spill area and cross it
to determine how far the spill had spread laterally, to what soil depths,and the
areas of high concentration of the chemical. A sample of undamaged soil should
also be taken. The samples should be sealed in containers, cooled and returned
to a laboratory for immediate analyses The following analyses are recommended
chemical concentration
soil pH
exchangeable sodium percentage
electrical conductivity
soil bacteria and actinomycetes
Soil pH, exchangeable sodium, electrical conductivity, and populations
need only be performed on a few of the samples, i.e., two from the areas of high
concentration of the spilled chemical, two from the fringes of the spill area,and
one from undamaged soil. Procedures for these analyses can be found in stan-
dard reference texts.
The results of these analyses will help determine the amount of damage
done to the soil by the spill and provide useful information to help in the
decision on the restoration technique to be used.
SELECTION OF THE APPROPRIATE LAND RESTORATION TECHNIQUE
A flow diagram to aid the On Scene Coordinator (OSC) in selection of
appropriate land restoration techniques for a particular spill situation is
presented in Figure 57. It must be remembered that this guide is very preliminary
in that it is based on a limited number of actual land restoration attempts and
laboratory experiments This flow chart should be updated as more information
becomes available and can be catalogued for each chemical.
APPLICATION OF THE LAND RESTORATION TECHNIQUE
Each of the potential land restoration techniques shown in Figure 57 and
Table 61 have many variations which can be modified to fit a specific spill
situation. The application of the techniques and potential modification thereof
are discussed in the following sections
223
-------
[«XKAl
lii Soil
Volatile Fro* Son.
Hazars T9
Ground o*
Surface
Haters
1q
ro <3110(010
Oft SURFACE
(foURS
HAS „J
I 1
tUlAUD TO
Crcmi»o Oft
SuRTACE
V«TEKS
>>![» Iimii
r~^
KO HaIARO
it Ground
o* SimfACc
INTERS
IUZA*» TO CcOUtO
or Surface Vahih
lb lUiAJto ro
Ground qr
Surface Waters
Cut Off
UtCHbNG
TO SURFACE
OR fiROlKD WftHR
i r~n i
PlQIOOCfiUbATIOM
to Les» Tome
ten CtVIRtM-CIIAL
°Ea$isic*T fqrh
Hichl* Acidic BiootwAUARLt Tome
CflHFollL Owmhim Hetals
t I
CmEAKAUY
*UAcrivc io
Less lout
Less Lt/iihw-
B100CSSADAU.E
Hiih 4cameo
*klTANT OR
GCfcCllCALlT
Contain
Toxic
Ieials
EaSJL* "teffE fllFFJCutr
DecRADA&lC To MCRADC
Bio-usable
Ihokanics
WNTAi FEUJII- Caqimeered
TEH1 roftfl CuLIURCt
I \
'lo Tovtc
Soil.
HtO COMCLHlRAt l(rn
Figure 57. Logic tree for selection of appropriate restoration techniques
-------
IA, IB. No Specific Land Treatment
For those compounds which readily volatilize from the soil or which are
non-toxic to the soil in high concentrations and easily biodegraded, no specific
treatment is necessary for removal of the chemical from the land. If the ground
water or surface water is endangered by the spilled material, IA, a barrier to the
transport of the material into these waterways will be necessary. This barrier
could take the form of a dam, grout curtain, etc. depending on the geology and
hydrology of the area If ground or surface water is not threatened, the material
should be allowed to escape from the soil naturally or be taken up by plants or
microorganisms. Revegetation of the area (VIII) may be necessary in some cases.
IIA, IIB, Biodegradation
Biodegradation is most applicable for water soluble, non-persistent,
organics (IIA) which are present in low concentrations (le3s than 1000 ppm). For
biodegradation of water soluble non-persistent organics, two methods can be used
- in situ biodegradation or washing the chemical out of the soil into a
biodegradation pond or ditch. In situ biodegradation can be accomplished by
repeatedly adding to the soil a mixed culture of organisms obtained from sewage
or from a biotreatment pond with nutrients, e.g., yeast extract, and minerals.
This process is continued until the concentration of the chemical contaminant has
been reduced to a safe level. The cost of this treatment is relatively low since
the only equipment necessary is a spray hose, pump and mixing tank
Removal of the chemical from the soil by flushing it into a biotreatment
pond provides a more rapid method of land restoration. The soil is cleansed
quickly and biodegradation occurs more rapidly in the aqueous media than in the
soil. This method is more expensive than in situ treatment.
The use of biodegradation to remove from the soil persistent chemicals
such as the chlorinated pesticides is a new technique which has potential for the
future. The organisms for degrading a specific chemical must be known and
immediately available. Identification of, or engineering of, specific cultures
of organisms to degrade these compounds requires future research. In addition,
for these organisms to be useful in a spill situation, they must be stored in an
accessible location for immediate culturing.
Neutralization
Acidic or basic compounds may only require neutralization for restoration
of the land or neutralization may be required to convert the chemical to a more
biodegradable form The neutralization techniques employed depends on the
compound. Previously used in situ soil neutralization methods include the
addition of lime for neutralization of acids and the addition of alum for
neutralization of caustic chemicals. Other techniques may be employed after
neutralization, e.g biodegradation, revegetation
Vegetative Uptake
The use of vegetation to remove metals and some organics from the soil is
an inexpensive method of land restoration. The method is slow, requiring several
225
-------
growing seasons and harvesting and disposal of Che plant tissue. It is most
useful for areas where ground or surface water contamination is not a problem.
Plants selected for this restoration method must be able to accumulate the
metal or organic, and grow well under the climatic conditions and soil conditions
of the spill site. Grasses and grains are probably the most useful plants for
vegetative uptake. Most are hardy, tolerate and grow well under a variety of
climatic and soil conditions. For the method to work well, soil pH should be
optimized to increase metal availability. A chelating agent should also be
applied periodically to aid in the plant uptake.
V, Physical Removal
For highly persistent or toxic compounds spilled on valuable land, or in
situations where the spill threatens water sources, the only alternative may be
physical removal of the chemical from the soil. Several types of physical
removal have been employed to treat land damaged by spills of hazardous
chemicals:
1) dig up the soil, package and send to an approved
hazardous landfill; refill with uncontaminaced soil
and revegetate
2) dig up and process the soil to remove the chemical;
degrade the chemical in the extract, return the soil
and revegetate
3) extract the soil in situ by flushing with water, treat
the extract, e g. carbon adsorption and, revegetate
the soil
4) solidify the soil to prevent movement of toxic
chemicals
Methods 1-3 all remove the material from the soil, however, they are very
expensive Method 4 simply scops the movement of the hazardous material until a
proper treatment methodology can be found.
VI, Chemical Reactions
In situ chemical reactions (other than neutralization) can degrade some
persistent chemicals to the point where natural degradation processes can take
over This type of treatment must be evaluated on an individual spill basis The
damage the reactant will do to the soil must be carefully assessed, so as not to
cause more damage than the original spill
VII, Optimization of Photodegradation
Photochemical degradation of persistent organics, e.g , polychlorinated
organics, has long been overlooked as a viable method of degrading these
chemicals in the environment. This technique works best on soils that are non-
226
-------
porous and retain the spilled material in the top layer. For this technique to
be useful, photodegradation conditions must be optimized as soon after the spill
as possible. Usually the only optimization process needed is to provide a
hydrogen donor source This source can be in the form of a biodegradable oil,
e.g. , olive oil. Another optimization procedure which can be used in addition to
the adding of the hydrogen donor source is adjustment of pH, usually to the basic
range. The photodegradation of many poly-halogenated compounds under these
optimization conditions will proceed rapidly if sunlight is available and rain
does not wash the chemical into the soil.
VIII, Revegetation
After the spill clean-up, during and after land restoration steps must be
taken to prevent the damaged soil from eroding. If the land is toxic to plants,
a mulch material such as straw, burlap can be applied to the area to lessen
erosion. As soon as the land will support vegetation, revegetation of the area
is suggested. Plants which could be used for revegetation are listed in Table 62.
227
-------
TABLE 62. VEGETATION RECOMMENDATIONS TO COVER LAND CONTAMINATION
WITH HAZARDOUS MATERIALS
Soil
Plant
Adaotation
Alkaline, Ult
Contaaiaated Soil*
Crown Vetch, Cornill* Varit
Leiptdttis, LeApedeu sp
Rye, Seceie cereaio
Beideiniiry (rin,
Prtaiaxi* aruitdkuca*
Barlev, Bordiua vulgar*
Till Wheatgrais,
Affropyron tldingttoa
western uheatgraaa,
A?ropyraA talzAii
Bercuda grata,
Qyrtodon daczylca
Birdifoot trefoil,
Lotus comicuiacus
Cotton, Gassypiun tiirsuzaa
Reedeanery grata,
Ptiaiarls arurrfinacea
Tall Nicut,
reatvca erundln*ce*
drought tolerant, cool aaaaon
vara aaaaon
cool seaaon
cool season, drought colaranc
adapted to vary wet condition*
drought tolerant, vara aaaaon
cool laaaoo
vara laaaon, poorly drained
aoila
vara season, dry aoila
vara seaaon, drought tolerant
cool season, drought toleraot
waro leaaon, draught tolerant
cool season, drought tolerant
adapted to very wet condition*
cool season
*fetal Contaainaced
Brovncop, Ayroatia fenis
cool
icaaon
Bad Fescue, feature Rubra
cool
•eaaon.
shade grass
Sarlev, ffordeua /uIgara
cool
season
Giant Bereuda grass,
warn
season,
drought colerane
Cynddcn Daczylan
Bye, Secaie Cereaio
cool
seaaon
228
-------
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234
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APPENDIX A
BACKGROUND DATA ON HAZARDOUS CHEMICALS
USED IN LABORATORY TESTS
MONOCHLOROBENZENE
Monochlorobenzene is a high production chemical which is used as a solvent
and as an intermediate in phenol, aniline, chloronitrobenzene and pesticide
manufacture. This chemical is currently produced by six U S. companies (SRI,
1979).
Product
Allied Chemical Corp
Indust. Chem. Division
Dow Chemical U.S.A.
Monsanto Co.
Monsanto Intermed. Co
Montrose Chem. Corp. of
California
PPG Indust., Inc.
Chem. Group
Chem. Division - U.S.
Standard Chlorine Chem
Company, Inc.
Location
Syracuse, NY
Midland, MI
Sauget, IL
Henderson, NE
Natrium, WV
Delaware City, DE
Annual Capacity
Millions of kg (lbs)
9.1
99.8
68.0
31.8
40 8
68 0
( 20)
(220)
(150)
( 70)
( 90)
(150)
Total U.S production capacity is 318 million kilograms (700 million pounds)
per year.
The pertinent physical, chemical and biological properties of monochloro-
benzene are listed in Table A-l. Based on these properties and its large
production volume, monochlorobenzene was chosen as a representative compound for
evaluation of techniques to restore spill damaged land.
ETHION
ETHION (0,0,0',0'-tetraethyl-S, S'-methylene biphosphorodithioate) is an
235
-------
TABLE A-l. PHYSICAL CHEMICAL AND BIOLOGICAL PROPERTIES OF
MONOCHLOROBENZENE (VERSCHUEREN, 1977)
Molecular Formula:
Structural Formula:
Molecular Weight:
Physical Form @ 20°C:
Odor:
Melting Point:
Boiling Point:
Vapor Pressure:
Vapor Density:
Specific Gravity:
Water Solubility:
Biological Degradation:
bod5
Biological Effects:
C6H5C1
~ CI
112.56
colorless liquid
honey suckle
-45°C
132°C
1170 Pa (8.8 torr) @ 20°C
1570 Pa (11.8 torr) @ 25°C
1940 Pa (15 torr) @ 30°C
3.88
1.1066
500 mg/1 @ 20°C
488 mg/1 @ 30 C
100% ring disruption of 200 mg/1 by
Pseudomonas in 58 hours
0.03 standard dilution sewage
bacteria: inhibition of cell
multiplication of Pseudomonas
putida@ 17 mg/1
algae: inhibition of cell
multiplication of Microcystes
aeruginosa @ 120 mg/1
fish: fathead minnow TLm 29-39
mg/1 (24-96 hours)
mammals: cat: inhalation LC 50 - 8000
ppm, 30 minutes
rat: inhalation LC50 - 12,000
ppm, 30 minutes
rat: oral LD50 - 2190 mg/kg
rabbit: oral LD50 - 2830 mg/kg
man: severe toxic effects at
400 ppm (1872 mg/cm,
60 minutes) unsatis-
factory - >75 ppm
(35.1 mg/cm, 60 minutes)
236
-------
insecticide and miticide manufactured by FMC Corporation, Agricultural Chemical
Division, Baltimore, Maryland. ETHION is used for mites on cotton, forage,
ornamentals, citrus, deciduous fruits, turf grasses and vegetables As a general
insecticide, ETHION can be used on 37 different food crops, cotton, sorghum and
other plants.
The chemical and physical properties of ETHION presented in Table A-2.
Toxicity data on ETHION are presented in Table A-3.
FORMALDEHYDE
Formaldehyde is used in the United States in the production of resins, as a
starting material for chemical production, as a fumigant, and as a tissue
preservative. Formaldehyde is currently manufactured by 16 U.S companies at 54
sites (SRI, 1979) The producer, location and capacity of the plants for
formaldehyde production are presented in Table A-4.
Formaldehyde is transported in large amounts on railroads, highways and
waterways. It is usually shipped at a 37-40% concentration in water stabilized
by the addition of 12—16% methanol. Because of formaldehyde's large use, the
probability of it being spilled is high. Formaldehyde is on the Coast Guard's
CHRIS List of Hazardous Chemical Data and is designated as a hazardous material
by the EPA (Federal Register, 1978). Data on the physical, chemical and
biological properties of formaldehyde are listed in Table A-5. These data
indicate that a formaldehyde spill would kill the lower animals and plants and
extensively harm higher animals
ANILINE
Aniline is used in the manufacture of dyes, medicinals, resins, varnishes
and perfumes. The estimated annual production of aniline is presented in Table
A-6. A total of approximately 499 million kilograms (1100 million pounds) of
aniline are produced per year at seven plants across the United States. The
physical and chemical properties of aniline are presented in Table A-7.
CHLORDANE
Chlordane (0ctachloro-4.7-methanotetrahydroindane) (Octachlorohexahydro-
methanoindene ) (1,2,4,5,6,7,8,8-0ctachloro-3a,4,7,7a-tetrahydro-4,7-methanoin-
dan) is a pesticide and is manufactured by the Velsicol Chemical Corporation in
Marshall, Illinois.
The physical and chemical properties of chlordane are presented in Table A-
8.
DINITROPHENOL
Dinitrophenol is used in the production of dyes and in preserving timber
This chemical is currently produced by 2 U. S. companies (SRI, 1980)
237
-------
TABLE A-2 CHEMICAL AND PHYSICAL PROPERTIES OF ETHION
(FMC, 1979)
American Standards Common Name:
Chemical Naqie:
Chemical Structure:
Empirical Formula:
Molecular Weight:
Appearance:
Odor:
Density:
Freezing Point:
Solubility at 20°C:
Vapor Pressure:
Stability:
Flammability:
Explosive Hazard:
Analytical Method:
ETHION
0,0,0',0'-tetraethyl S,S'-methylene
bisphosphorodithioate
ch3ch2on
ch3ch2o
P-S-CH2-S
s /
4/
0CH2CH3
^OCH2CH3
C9H22°4P2S4
384
Water white to amber colored liquid
Typical phosphate insecticide odor
1.215 to 1.230 at 20°C
-12°C to -15°C
Water 2 ppm
Organic Solvents
Acetone Miscible
Chloroform Miscible
Kerosene Miscible
Methylated
Naphthalene Miscible
Xylene Miscible
2.0 x 10"4 Pa (1.5 x 10~6 torr) at 25°C
Subject to slow oxidation in air,
hydrolysis to acids and bases
Not flammable
Like other phosphate and thiophosphate
esters, ETHION may decompose explosivelv
o
at temperatures above 150 C
Formulations: IR Method
Residues: Detection by flame photometric
gas chromatograph
238
-------
TABLE A-3. TOXICOLOGY OF ETHION
(FMC, 1979)
Biological Effects: - Mammalia:
rat: oral LD50 (mg/kg)
Technical 70-119
25% Wettable Powder 600
Emulsifiable Concentrate
(4 lbs Ethion/gal) 400
Ethion (2%) Dormant Oil Spray 6800
rat: inalation LD50 (mg/1 air)
25% wettable powder 72,000
rat: intraperitoneal LD50 (mg/kg)
Ethion 4 EC 147
rabbit: dermal LD50 (mg/kg)
Technical 915
25% Wettable Powder 2172
Emulsifiable (4 lbs Ethion/gal) 2300
Ethion (2% Dormant Spray) 6800
rabbit: eye irritation
Ethion - nonirritant
- Fish: Bluegill static
96 hr LD50 95 ppb
- Wildlife - Oral LD50 (mg/kg)
male female
Bobwhite quail 74 73
Japanese quail 234 302
Mallard duck 1600 1600
- Man: Ethion is a cholinesterase inhibitor. Ear-
ly symptoms are headache, weakness, excess
perspiration, nausea, blurring vision, and
tightness in chest. Later symptoms include
vomiting, abdominal cramps, muscular twitch-
ing, diarrhea, and coma.
Chronic intoxication may or may not produce
symptoms. Chronic intoxication is serious in
that a minor additional exposure may lead to
an acute serious episode of intoxication due
to asymptomatic cumulative depression of
choline-esterase activity.
239
-------
TABLE A-4. PRODUCTION AND CAPACITY OF FORMALDEHYDE IN THE UNITED STATES
(SRI, 1979)
Annual
Capacity
Producer Location
Millions of kg (lbs'
Allied Chem. Corp.
Specialty Chems. Div. South Point, OH
140 .6
(310)
Borden Inc.
Borden Chem. Div.
Adhesives and Chems. Div. -
East Demopolis, AL
45.4
(100)
Diboll, TX
36.3
(80)
Fayetteville, NC
106.6
(235)
Louisville, KY
36.3
(80)
Sheboygan, WI
59.0
(130
Adhesives and Chems. Div. -
West Fremont, CA
102.0
(225)
Kent, MA
36.3
(80)
La Grande, OR
29.5
(65)
Missoula, KI
40.8
(90)
Springfield, OR
108.9
(240)
Petrochems Geistnar, LA
113.4
(250)
Celanese Corp.
Celanese Chem. Co., Inc. Bishop, TX
680.4
(1500)
Newark, NJ
53.1
(117)
Rock Hill, SC
53.1
(117)
E I du Pont de Nemours & Co.,Inc.
Chems., Dyes and Pigments Dept. Belle, WV
226.8
(500)
Healing Springs, NC
99.8
(220)
La Porte, TX
145.1
(320)
Linden, NJ
71.6
(160)
Toldeo, OH
122.5
(270)
GAF Corp.
Chem. Products Calvert City, KY
45.4
(100)
Georgia-Pacific Corp.
Chem. Div. Albany, CR
59.4
(120)
Columbus, OH
90.8
(200)
Coos Bay, OR
40.8
(90)
Crossett, AR
72.6
(160)
Lufkin, TX
47.4
(100)
Russelville, SD
90.8
(200)
Taylorsville, MS
54.4
(120)
V ienna, GA
45.4
(100)
(continued)
240
-------
TART.F. A-4. ( rnnr i nnpri 1
Annual Capacity
Producer Location Millions of kg (lbs)
Getty Oil Co.
Chembond Corp., subsid
Gulf Oil Corp
Gulf Oil Chem. Co.
Indust & Specialty Chem. Div,
Hercules Inc.
International Minerals &
Chem. Corp.
IMC Chem Group
Monsanto Co.
Monsanto Plastics & Resins Co
Occidental Petroleum Corp.
Hooker Chem. Corp., Subsid.
Hooker Chem. and Plastics Corp
subsid.
Andalusia, AL 31.8 (70)
Springfield, OR 63.6 (140)
Wmnifield, LA 31.8 (70)
Vicksburg, MS 20.4 (45)
Louisiana, MO 77.1 (170)
Wilmington, NC 45.4 (100)
Seiple, PA 79 5 (65)
Sterlington, LA 13.6 (30)
Addyston, Ohio 45.4 (100)
Chocolate Bayou, TX 88.5 (195)
Eugene, OR 45 4 (100)
Springfield, MA 133 8 (295)
Durez Div
North Tonawanda, NY
61.2
(135)
Reichhold Chem., Inc.
Hampton, SC
22.7
(50)
Houston, TX
54.4
(120)
Kansas City, KS
22 7
(50)
Malvern, AR
49.9
(110)
Moncure, NC
54.4
(120)
Tacoma, WA
21.8
(48)
Tuscaloosa, AL
32 7
(72)
White City, OR
113.4
(250)
Tenneco Inc.
Tenneco Chem , Inc
Fords, NJ
83.9
(185)
Garfield, NJ
45 4
(100)
Univar Corp.
Pacific Resins & Chem., Inc.,
subsid Eugene, OR
(continued)
43.1
(95)
241
-------
TABLE A-4 (continued)
Producer
Location
Annual Capacity
Millions of 1® (lbs)
Wright Chem. Corp Acme, NC 76.3 (80)
TOTAL 4116.1 (9074)
Note- Capacity figures are on a 37% basis
Source: SRI International estimates
242
-------
TABLE A-5. PHYSICAL, CHEMICAL AND BIOLOGICAL PROPERTIES OF
FORMALDEHYDE (VERSCHUEREN, 1977)
Molecular Formula:
Structural Formula:
Molecular Weight:
Physical Form @ 20°C:
Odor •
Melting Point.
Boiling Point :
Vapor Pressure.
Vapor Density
Specific Gravity:
Commercial Formaldehyde
Solution
HCHO, wt%
Boiling Point
Density at 18°C
Flash Point
Air Pollution TLV :
BOD 5 :
Biological Degradation:
Biological Effects:
HCHO
0
H-fi-H
30 0
gas
hay, strawlike, pungent
-92°C
-19°C
1330 Pa (10 torr) at -88°C
1.03
0.815 at 4°C
37
98.9
1.11 g/ml
85 .0°C
3 ppm (USA)
0.33 - 1.06 std. dil. sewage
+ 1/2 02_»CH00H *1/2 »2 C02 + H20
HCHO
* CH3OH +J_1Z1»°2 C02 + 2h20
Bacteria E coll. Toxic: 1 mg/1
Pseudomonas putida inhibition of cell
(continued)
243
-------
TABLE A-5 (continued)
- multiplication starts at 0.39 mg/1 for a
35% solution
- Algae: Scenedesmus: Toxic: 0.3-0.5 mg/1
Microcystis Aeruginosa: inhibition of cell
multiplication starts at 0.39 mg/1 for a
35% solution
- Arthropoda: Daphnia: toxic: 2 mg/1
- Fish-
sensitive aquatic organisms: TLra
50-2000 mg/1
Mammalia•
guinea pig: single oral LD50. 0.26 g/kg
rat. single oral LD50: 0.1-0.8 g/kg
rat: inhalation: LC50* 250 ppm, 4 hr.
830 ppm, 30 rain.
cat- inhalation: LC50: 650 ppm, 8 hr.
all survived:
200 ppm, 3.5 hr
- Man:
severe toxic effects: 100 ppm=120 mg/cu
m, 1 min.
symptoms of illness: 30 ppm= 36 mg/cu m
unsatisfactory: 10 ppm= 12 mg/cu m
244
-------
TABLE A-6. ESTIMATED ANNUAL PRODUCTION OF ANILINE IN THE UNITED STATES
Producer
Location
Annual Capacity
Millions of Kilo-
grams (pounds)
Raw Material
American Cyanamid Co.
Organic Chemi Div.
Bound Brook, N.J.
Willow Island, W. Va.
37.2
22. 7
(60)
(50)
Nitrobenzene
Nitrobenzene
E.I. du Pone de Nemours & Co., Inc.
Chemi. Dyes and Pigments Dept.
Beaumont, Tex.
Gibbstown, N. J.
104 3
77. 1
(230)
(170)
Nitrobenzene
First Mississippi Corp.
First Chem. Corp. Subsid.
Pascagoula, Miss.
113.4
(250)
Nitrobenzene
"Mobay Chem. Corp.
Indust. Chem. Div.
New Martinsville, W. Va.
45 4
(100)
Nitrobenzene
Rubicon Chem Inc.
Ceismar, La.
127
(280)
ICI Process
TOTAL
517.1 (1,140)
-------
TABLE A-7. PHYSICAL AND CHEMICAL PROPERTIES OF ANILINE
Molecular Formula.
C6H5NH2
Structural Formula:
<0^
nh2
Molecular Weight:
93.1
Physical Form @ 20°C*
liquid
Melting Point.
-6°C
Boiling Point.
184° C
Vapor Pressure.
133 Pa (1
40 Pa (.3
torr) at 35°C,
torr) at 20°C
Vapor Density
3.22
Specific Gravity:
1.02
Solubility:
Water
34,000 mg/1
Alcohol
miscible
Benzene
miscible
Chloroform miscible
246
-------
Table a-8. physical and chemical properties of chlordane
Molecular Formula: C1r.H,Cl0
10 6 8
Structural Formula
Molecular Weight
Physical Form @ 20°C Amber-colored liquid
409.8
Density
1.59-1.63 at 25°C
Solubility
Insol. in water
Miscible in aliphatic and
aromatic hydrocarbons
247
-------
Producer
Location
Martin Marietta Corp
Martin Marietta Chem
Sodyeco Division
Mobay Chem. Corp
Dyestuff Division
Indust. Chem. Division
The physical, chemical and biological
presented in Table A-9.
LEAD NITRATE
Sodyeco, NC
Bushy Park, SC
Bushy Park, SC
properties of dinitrophenol are
Lead which is used as a mordant in dyeing and printing calico, matches, paint
pigment, mordant for staining mother of pearl, oxidizer in the dye industry,
sensitizer in photography, explosives, tanning, process engraving, and litho-
graphy. Lead nitrate is manufactured by the following companies.
Producer Location
Richardson-Merrell, Inc.
J.T. Baker Chem. Co. sub. Phillipsburgh, NJ
G. Frederick Smith Chem. Co. Columbus, OH
The physical and chemical properties of lead nitrate are presented in Table
A-10.
CADMIUM NITRATE
Cadmium nitrate is used as a starting material for nickel-cadmium and
silver-cadmium alkaline storage batteries. Generally cadmium is used in the
electroplating industry and batteries. Cadmium nitrate is manufactured by the
following companies
Producer Location
Allied Chem. Corp
Chem. Co. Buffalo, NY
Marcus Hook, PA
W.A. Cleary Corp. Somerset, NJ
Gulf Oil Corp.
Harshaw Chem. Co. sub.
Indust. Chem. Dept. Cleveland, OH
The Hall Chem Co. Arab, AL
McGean Chem Co., Inc. Cleveland, OH
248
-------
TABLE A-9. PHYSICAL, CHEMICAL AND BIOLOGICAL PROPERTIES OF DINITROPHENOL
(VERSCHUEREH 1977)
Molecular Formula:
Structural Formula
Molecular Weight
Physical Form @ 20°C
Melting Point
Vapor Density
Specific Gravity
Water Solubility
, AIR POLLUTION FACTORS: 1 mg/cum=0.13 ppm, 1 ppm = 7.65 mg/cu m
—T.L.V.: USSR: 0.007 ppm = 0.05 mg/cu m 1971 (n.s.i.)
WATER POLLUTION FACTORS:
—Water quality:
M.A.C. in waters class I for the production of drinking water: 0.03 mg/1
—Biodegradation:
adapted culture: 2% removal after 48 hr incubation, feed: 200 mg/1
adapted A.S. at 20°C—product is sole carbon source: 85.0% COD removal
at 6.0 mg COD/g dry inoculum/hr
—Impact on biodegradation processes:
inhibition of degradation of glucose by Pseudomonas fluorescens at:
3 mg/1
inhibition of degradation of glucose by E.- at: >100 mg/1
BIOLOGICAL EFFECTS:
—Bacteria:
E_. coli; toxic: 100 mg/1
Pseudomonas putida; inhibition of cell multiplication starts at 115 mg/1
—Algae:
Scenedesmus: toxic: AO mg/1
Microcystis aeruginosa: inhibition of cell multiplication starts at 33 mg/1
—Arthropoda: Daphnia; toxic: 6 mg/1
—Man: unsatisfactory: >1 mg/cu m (n.s.i.)
(no2)2 c6h3oh
NO
HO-
184.11
Yellow rhombic crystals
111-114°C
6.36
1.683 at 24°C
5600 mg/1 at 18°C
43000 mg/1 at 100°C
249
-------
TABLE A-10- PHYSICAL, CHEMICAL AND BIOLOGICAL PROPERTIES OF
LEAD NITRATE (HAWLEY, 1977)
Molecular Formula
Molecular Weight
Physical form @ 20°C
Melting Point
Boiling Point
Specific Gravity
Solubility
Biological Effects:
Pb(N03)2
331.2
White crystals
Decomposes at 470°C
4.53
Water 37.65 g/100 cc at 20°C
Rat, oral LDLo: 432 mg/kg
intravenous LDLo: 50 mg/kg
250
-------
Richardson-Merrell, Inc
J T Baker Chem Co sub Phillipsburg, NJ
The Shepherd Chem Co Cincinnati, OH
United Catalysts Inc Louisville, KY
The physical and chemical properties of cadmium nitrate are presented in
Table A-ll.
TABLE A-ll. PHYSICAL, CHEMICAL AND BIOLOGICAL PROPERTIES OF CAMIUM
NITRATE (HAWLEY, 1977)
Molecular Formula:
Molecular Height:
Physical Form @ 20°C:
Melting Point:
Boiling Point:
Specific Gravity:
Solubility:
Biological Effects:
Cd(N03)2
236.41
white, amorphous pieces
350°C
2.455
Water 109 g/100 cc at 20°C
Ammonia soluble
Alcohol soluble
Rat, oral LD50: 300 mg/kg
251
-------
APPENDIX B
MONOCHLOROBENZENE DATA
This Appendix contains additional supplemental data obtained on land
restoration techniques for the monochlorobenzene spill. The following data are
included in this Appendix.
background soil analyses
•pH of soils as a function of core depth and time
•percent moisture of soils as a function of core
depth and time
bacterial population in the middle and lower soil
layers
252
-------
TABLE B-l. BACKGROUND ANALYSES OF SOILS IN MONOCHLOROBENZENE SPILL
Property Measured
Depth
(era)
High Organic
Soi 1
Sandy-Loam
Clay Soil
pll
0 5
6 5
6 3
5 5
5-10
6 05
6 3
4 95
10-30
5 8
5 95
5 35
51 Hols Cu re
0-5
5 96
0 89
0 69
5-10
0.75
I 46
0 52
10-30
1 29
I 19
1 19
X Oiganic
0-5
16 56
5 25
2 63
5-10
4 19
4 87
3 45
10-30
0 6
0 77
0 48
NlLiilte N (ppm)
0-5
0.76
0 5
0 48
5-10
0 76
U 44
0.48
10-30
0 6
0 77
0 48
Tola 1 Phosphorus (ppm)
0-5
60.0
13 0
19.0
Potassium (ppm)
0-5
55 0
139 0
45 0
Ca1llum (ppm)
0-5
624 0
1200.0
708 0
Mdgncsium (ppm)
0-5
57 0
120 0
107 0
-------
TABLE B-2.
pH OF HIGH
ORGANIC
SOIL CORE
: SEGMENTS -
MONOCHLOROBENZENE
SPILL
Depth
(cm)
Initial
1
2
Days
8
15
22
29
41
Control
0-5
6.5
7.9
7.8
7.7
7.7
6.5
8.9
8.3
5-10
6.05
6.9
6.3
6.7
7.5
6.2
7.3
7.3
10-30
5.8
7.4
6.3
6 9
7.0
7.4
6 7
6.8
T-l
0-5
*
7.7
8.7
7.4
8.4
8.9
8.9
9.1
5-10
*
6.6
6.3
7.2
8.4
7.4
7.6
7.8
10-30
*
7.2
6.6
7.1
7.6
7.0
6 7
7 0
T-2
0-5
*
7.4
7.4
8.0
8.5
7.2
8.6
8.0
5-10
6.8
6 3
7.9
7.9
6.9
8.2
7.3
10-30
&
6.2
6.3
7.4
7.4
6.9
7.3
6.7
254
-------
TABLE B-3. pH OF SANDY-LOAM SOIL CORE SEGMENTS - MONOCHLOROBENZENE SPILL
Depth
(cm)
Initial
l
2
8
Days
15
22
29
42
Control
0-5
5.8
6.4
6.2
6.8
7.1
6.1
7 1
6.4
5-10
6 3
7.4
6.8
6.7
6 7
6.4
7 1
6.8
10-30
6.0
7 6
7 0
6.8
6 3
5.8
6.5
7.3
T-l
0-5
*
7.1
6 8
6.9
7 5
6.8
6.9
7 0
5-10
it
6 8
6.3
7.0
7.1
6.7
6.3
6.5
10-30
*
7 3
6.7
7 1
7.2
6 9
6.8
6 5
T-2
0-5
ir
7.3
6.5
7.5
7 2
6.9
6.5
6.1
5-10
it
6.6
7.0
6.6
6.9
6.7
7.0
6.4
10-30
it
7 0
6.9
6.5
7.1
7.2
7 1
7.0
Assumed to be similar to control
255
-------
TABLE B-4 pH OF CLAY SOIL CORE SEGMENTS - MONOCHLOROBENZENE SPILL.
Days
Depth
(cm) Initial 1 2 8 15 22
29 42
Control
0-5 5.5 6.2 6.1 6.4 6.2 5.7 6.0 6.2
5-10 5.0 6.4 6.2 6.0 6.2 5.6 5.9 5.8
10-30 5.4 6.2 6.5 6.2 6.6 5.2 6.6 5.6
T-l
0-5 * 6.0 5.9 6.4 7.0 5.9 6.1 6.1
5-10 * 6.2 6.4 6.1 6.9 5.3 5.8 6.6
10"30 * 6.0 6.5 5.7 7.3 5.5 5.5 5.2
T-2
0-5 * 6.1 6.1 5.9 6.9 6.3 5.9 6.2
5-10 * 6.3 6.4 6.2 6.7 5.7 7.6 6.2
10-30 * 6.2 5.4 6.1 6.7 6.2 6.3 6.3
* Assumed to be similar to control
256
-------
TABLE B-5. PERCENT MOISTURE CONTENT HIGH ORGANIC SOIL
MONOCHLOROBENZENE SPILL
Depth
(cm)
Initial
1
2
Days
8
15
22
29
42
Control
0-5
9.0
24.5
35.0
10.1
-
-
13.9
11.8
5-10
11.7
17.3
36.5
11.5
12.2
14.2
"9.0
"5.4
10-30
11.2
16.8
13.7
13.3
9.7
22.0
15.9
3. 5
T-l
0-5
*
43.7
30.1
23.1
32.4
48.6
26.3
63.0
5-10
*
20.7
20.9
21.2
19.9
34.8
23.3
16.4
10-30
*
27.3
18.1
19.1
19.2
6.9
23.2
14.8
T-2
0-5
5-10
10-30
19.8
18.5
17.8
22.9
16.1
23.7
17.4
19.6
16.2
14.8
14.0
12.1
17.7
10.4
13.5
26.0
22.2
19.3
25.3
11.2
17.1
* Assumed to be similar to control
All chambers watered after sampling on day 15 and day 29.
257
-------
TABLE B-6. PERCENT MOISTURE CONTENT SANDY LOAM SOIL-
MONOCHLOROBENZENE SPILL
Depth
(cm)
Initial
1
2
Days
8
15
22
29
42
Control
0-5
9.6
11.2
20.8
11.7
7.8
14.1
477
-
5-10
8.4
14.5
11.3
11.1
6.6
11.2
19.6
12.2
10-30
13.3
23.3
15.7
15.1
14.6
13.5
7.4
19.6
T-l
0-5
*
13.8
13.5
11.6
11.5
27.7
14.7
20.3
5-10
*
10.9
15.4
19.3
17.8
25.6
-
21.3
10-30
*
14.2
18.8
13.0
12.3
23.1
22.3
12.4
T-2
0-5
*
13.5
15.9
14.0
17.0
20.7
23.7
-
5-10
*
14.7
15.1
20.6
13.0
20.1
17.2
35.9
10-30
*
14.3
15.2
15.8
17.1
18.4
19.6
19.2
* Assumed Co be similar to control
All chambers watered on days 15, 22, and 29 after sampling
258
-------
TABLE B-7 . PERCENT MOISTURE CONTENT CLAY SOILS -
MONOCHLOROBENZENE SPILL
Depth
(cm)
Initial
i
2
Days
8
15
22
29
42
Control
0-5
7.3
8.3
18.4
14.9
10.4
23.0
15.2
15.7
5-10
5.1
15.2
17.3
13.9
12.7
6.8
17.2
19.5
10-30
10.0
13.5
15.5
17.0
27.3
24.3
12.2
16.4
T-l
0-5
*
14.4
14.0
7.7
13.0
15.2
11.8
14.8
5-10
*
8.3
12.5
13.9
14.0
16.3
13.7
16.0
10-30
*
16.6
14.3
14.5
17.8
20.1
7.4
24.4
T-2
0-5
*
9.7
18.0
11.3
21.4
6.6
15.4
5.3
5-10
*
16.4
20.6
15.1
20.8
31.6
16.0
17.5
10-30
it
13.6
19.3
7.7
14.9
-
29.0
9.9
* Assumed to be similar to control
All chambers watered on days 15, 22 and 29 after sampling.
259
-------
TABLE B-8. PERCENT ORGANIC CONTENT HIGH ORGANIC SOIL -
MONOCHLOROBENZENE SPILL
Depth
(cm)
Initial
1
2
Days
8
15
22
29
36
Control
0-5
16.6
15.6
17.4
13.0
10.5
-
16.1
17.7
5-10
4.2
5.5
5.4
3.9
4.2
5.1
5.8
8.3
10-30
2.9
4.8
4.6
4.8
4.1
11.5
5.5
2.1
T-l
0-5
*
14.8
17.8
12.7
15.7
28.7
12.2
54.3
5-10
*
3.4
5.5
4.2
3.3
6.2
6.5
4.0
10-30
*
7.6
4.6
3.8
-
4.3
5.6
4.0
T-2
0-5
*
7.1
9.6
12.7
12.0
10.4
17.0
10.2
5-10
*
4.3
4.2
2.4
3.7
4.8
27.0
4.4
10-30
*
4.2
4.1
4.2
4.9
4.8
-
4.0
* Assumed Co be the same as control
260
-------
TABLE B-9 PERCENT ORGANIC CONTENT SANDY SOIL - MONOCHLOROBENZENE SPILL
Days
Depth
(cm) Initial 1 2 8 15 22 29 36
Control
0-5 5.3 4.2 4.5 6.1 6.9 5.4 6.7 5.9
5-10 4.9 5.0 8.1 3.4 7.2 4.5 6.8 4.7
10-30 4.7 2.6 5.7 3.1 4.7 6.6 6.0 4.8
T-l
0-5
5-10
* 5.2 4.9 6.1 7.0 6.5 6.7 5.0
* 3.9 5.6 11.4 2.2 5.4 5.6 4.2
10-30 * 4.4 6.4 5.2 0.4 5.5 7.0 5.6
T-2
0-5 * 4.0 6.2 6.2 7.0 6.7 5.9 4.5
5-10 * 5.2 5.3 4.6 2.9 6.4 7.1 4.1
10-30 * 4.9 5.6 4.9 3.4 4.9 7.0 6.2
* Assumed to be similar to control
261
-------
TABLE B-10. PERCENT ORGANIC CONTENT CLAY SOIL - MONOCHLOROBENZENE SPILL
Days
Depth
(cm)
Initial
1
2
8
15
22
29
36
Control
0-5
2.6
1.5
2.7
2.3
3.0
2.9
4.3
3.7
5-10
3.5
1.5
2.3
2.2
-
4.4
4.3
2.0
10-30
4.7
1.8
2.4
6.8
3.0
3.9
4.1
3.0
T-l
*
2.5
4.5
2.8
3.7
4.9
1.8
0-5
*
_
1.9
1.9
2.2
3.8
4.6
3.5
5-10
*
2.7
1.9
3.5
3.6
4.2
3.0
10-30
T-2
0-5
*
3.1
2.9
3.6
3.0
5.4
4.8
1.7
5-10
*
3.0
3.8
4.5
-
3.6
4.9
0.1
10-30
*
3.0
5.5
11.4
-
4.5
4.5
2.0
* Assumed to be similar Co control
262
-------
BACTERIA
1,000,000--
z:
c
cc
o
0 CONTROL
cc
UJ
o_
A T-2
to
QC
LU
CD
s:
CO
100,000--
FUNGI
c.
o
C-
10,00i
-5 '0 5 10 15 20 25 30 35 40 45
TIME IN DAYS
Figure B-1. Middle level (5-10 cm) high organic soil
microbial population - monochlorobenzene spill.
263
-------
bacteria
o CONTROL
A T-2
«
ac.
is
100,000 -=
FUNGI
z
i-
<
Q.
a.
10,000 --
5 0 5 10 15 20 25 30 35 40 45
TIME IN DAYS
Figure B-2. Bottom level (10-30 cm) high organic soil
microbial population - monochlorobenzene spill.
264
-------
100,000,000
BACTERIA
O CONTROL
G T-1
A T-2
Lii
Q_
UJ
m
FUNGI
V
CO
Z
o
f—
100,000--
<
Z)
a
o
Q.
iT l i I i I i I i L-J~
-5 0 5 10 15 20 25 30 35 40 45
TIME IN DAYS
Figure B-3. Middle Level (3-10 cm) sandy-loam soil
microbial population - monochlorobenzene spill.
265
-------
BACTERIA
10,000,001
G CONTROL
~ T-1
A T-2
| 1,000,001
oc
a:
LU
00
a:
ID
to
100,000--.
FUNGI
-3- I I I I I i I i I T
-5 0 5 10 15 20 25 30 35 40 45
TIME IN DAYS
Figure B-4. Bottom level (10-30 cm) sandy-loam soil
microbial population - monochlorobenzene spill.
266
-------
o CONTROL
~ T-1
A T-2
6,000,000
1,000,000 —
<
a.
13
a.
UJ
Q.
(O
a
UJ
CD
100,000
3
0.
o
a.
10,000—I
BACTERIA
FUNGI
Figure B-5.
0 5 10 15 20 25^ 30 35 40 45
TIME IN DAYS
Middle Level (5-10 cm) clay soil microbial
population - moriochlorobenzene spill.
267
-------
10,000,000
1,000,000
<
CE
CD
a:
UJ
Q_
CO
0£
UJ
CO
s:
3
00
z
o
<
Q_
O
Q_
100,000
10,000--
o CONTROL
~ T-1
A T-2
BACTERIA
FUNGI
10 15 20 25 30 35
TIME IN DAYS
40 45
Figure B-6. Bottom level (10-30 cm) clay soil microbial
population - monochlorobenzene spill.
268
-------
APPENDIX C
ETHION DATA
This appendix contains additional supplemental data obtained on land
restoration techniques for an Ethion spill. The following data are included in
this Appendix.
•background soil analyses
•pH of soils as a function of core depth and time
•percent moisture of soils as a function of core
depth and time
•bacterial populations in the middle and lower soil
layers
•1*C radiation levels
269
-------
TABLE C-l. BACKGROUND ANALYSES OF SOILS - ETHION SPILL
Property Measured Depth High Organic
(cm) Soil Sandy-Loam Clay Soil
pH
0-5
7 3
6 5
6.35
5-10
7.6
6.7
6.4
10-30
6.7
7.0
6.3
% Moisture
0-5
9.6
7.3
9.0
5-10
8.4
5.1
11. 7
10-30
13.3
10.0
11.3
% Organic
0-5
7.6
5.1
1.9
5-10
3.9
5.0
2.2
10-30
3.2
4.2
2.0
Nitrate N (ppm)
0-5
0.3
2.5
0.7
5-10
0 3
0.3
0.3
10-30
0.7
0.3
0.3
Organic Phosphorus (ppm)
0-5
1.0
1.0
1.2
5-10
0.7
1.0
. 7
10-30
3.0
3.0
. 1
Total Phosphorus (ppm)
0-5
60
13
19
Potassium (ppm)
0-5
55
139
45
Calcium (ppm)
0-5
624
1200
708
Magnesium (ppm)
0-5
57
120
107
-------
TABLE C-2. pH OF ORGANIC SOILS CORE SEGMENTS - ETHION SPILL
DepCh
(cui)
Initial
1
2
9
16
23
30
17
AA
52
59
65
Control
0-5
7.3
A.7
5.9
6.5
5.05
6.25
6.05
5.25
3.85
5.2
5.A
5.9
5-10
7.6
6.0
5.2
A.75
A.15
5.A5
5.8
5.6
A.A5
5.A
5.9
A.5
10-30
«T> 1
6.7
A. A
6.A
5.1
A.A5
5.A5
5.8
5.85
4.95
A.7
5.85
A.6
1 - 1
0-5
*
5.2
5.1
6.05
6.05
6.1
6.2
5.56
A.25
6.3
6.0
6.6
5-10
*
5.1
A.7
5.25
A.75
6.75
5.95
A.75
A.A
5.3
6.A
6.2
10-30
*
6.1
A.65
A.5
A.35
5.85
A.85
A.A5
6.2
A.85
5.7
5.3
T-2
0-5
*
6.2
5.7
6.6
6.3
6.05
5.75
6.15
A.25
6.2
6.8
7.2
5-10
*
5.5
A.7
5.05
6.05
A.A5
6.15
6.0
A.5
A.9
5.6
6.7
10-30
*
6.6
5.05
5.25
5.75
A.8
A. A
5.35
6.05
5. A
6.6
5.0
* Assumed same as control
(continued)
-------
TABLE C-2 (continued)
Depth
(cm)
72
79
86
93
101
108
113
121
127
136
142
Control
0-5
5.7
5.3
5.2
5.15
5.45
4.8
5.1
4.7
4.3
5.1
5.5
5-10
5.4
5.2
5.0
5.25
5.0
5.0
4.95
4.7
4.1
5.4
5.45
10-30
5.2
5.2
5.0
' 5.0
5.0
4.6
4.85
4.9
4.0
5.0
5.2
T-l
0-5
5.7
7.3
5.2
5.15
5.45
4.8
5.8
5.9
4.65
5.7
5.5
Ui
1
O
5.4
5.2
5.0
5.25
5.0
5.0
4.9
4.8
4.60
4.45
5.2
10-30
5.2
5.2
5.0
5.0
5.0
4.6
5.0
5.15
4.3
4.45
4.7
T-2
0-5
6.5
7.1
6.85
6.3
6.45
6.1
6.45
6.0
5.5
5.85
6.15
5-10
5.5
5.25
5.8
5.25
5.2
4.6
5.3
4.9
4.85
5.3
5.25
10-30
5.7
5.2
5.8
5.1
5.0
4.8
4.9
4.8
4.45
4.7
4.55
(continued)
-------
TABLE C-2 (continued)
Depth
(cm)
155
158
183
186
205
210
212
219
1±\
228
238
249
Control
0-5
5.15
4.7
4.8
5.3
5.25
5.5
4.8
4.9
4.9
5.4
5.2
5.1
5-10
5.1
4.6
4.8
4.95
5.29
5.3
4. 7
4.8
-
5.9
5.1
5.0
10-30
T-l
5.0
4.5
4.9
5.0
-
-
-
4.7
-
-
5.1
5.0
: 0-5
6.1
6.2
7.9
9.8
10.30
10.4
9.9
8.6
9.6
9.8
9.75
10.3
5-10
5.6
4.8
6.9
7.1
10.40
10.5
10.3
6.3
-
8.2
9.2
10.3
10-30
5.05
4.7
5.4
5.5
-
-
-
5.5
-
-
10.2
9.45
T-2
0-5
6.0
5.8
6.3
5.7
6.80
6.6
11.2
12.5
11.5
10.6
11.7
10.7
5-10
5.6
5.4
5.85
5.1
5.30
5.3
8.1
10.8
-
9.9
10.75
10.4
10-J0
5.2
5.3
5.1
4.8
-
-
-
7.5
-
-
11.8
9.8
256
5. 2
5.2
5.05
10.2
9.1
9.1
12.4
10.6
6.4
-------
TABLE C-3. pH OF SANDY SOILS CORE SEGMENTS - ETHION SPILL
Depth
(cm)
Initial
i
2
9
16
23
30
37
44
52
59
65
Control
0-5
6.7
4.5
4.7
4.95
3.85
4.35
4.0
4.35
4.95
5.0
5.25
4.7
5-10
7.0
4.0
4.3
4.5
5.25
4 35
3.95
5.6
5.05
5.8
6.0
6 0
10-30
7.0
4.0
4.3
4.5
5.25
4.35
3.95
5.5
5.05
5.8
6.0
6.0
T-l
0-5
"tt
3 8
4.25
3.35
3.8
5.95
3.75
4.3
3.8
4.7
6.1
6.1
5-10
"ii
5.4
4.65
5.8
5.1
5.85
3.85
4.25
4.3
5.1
5.85
5.6
10-30
*
5 3
5.45
5.9
5.1
4.1
4.45
4.25
5.0
5.8
6.8
5.8
T-2
0-5
*
4.3
4 7
4.45
4.65
4.15
3 8
4.8
-
5.4
5.6
6.0
5-10
-
4.8
4.8
5 15
4.95
4.65
3.75
5 65
4.55
5.3
6.0
6.1
10-30
Vr
5.5
5.9
5.45
4.65
4.05
4.45
5.25
5.35
4.4
5.7
6.1
^'assumed
same as
control
(continued)
-------
TABLE C-3 (continued)
DepLh
(cm) 72 79 86 93
Control
0-5
5.4
5.3
3.35
4 6
5-10
5 4
4.75
5.4
4.8
10-30
5.6
5.1
5.6
5 1
-1
0-5
7.1
6.1
6.4
5.7
5-10
6 9
6 1
6.25
5.6
10-30
6.4
5.5
5 4
5 2!
-2
0-5
7.3
7.0
6.3
6.3
5-10
6 6
6 6
5.95
6.0
10-30
5.8
5 3
5.3
5.0
101 108 113
121
127 136
142
4 5
4.8
4.8
6 1
6.15
5.5
6.5
5.9
4.9
4.35
5.0
4 6
5 9
5.4
4.7
6.0
6 0
5.2
4.8
5.15
4.4
5.9
5.4
5.7
5.65
5 95
5.0
4.4
4.6
5 I
6 1
5.5
5.3
6.0
5.3
5.1
4.0
4.4
4.65
4.6
5.0
5 35
6.45
5.4
5 0
4.3
4.2
4 6
4.75
4.8
4.8
5.7
5.0
5.1
4.35
4 55
4.7
5.35
5.1
5.1
5.3
5.45
4.8
(continued)
-------
TABLE C-3 (continued)
Depth
(cm) 155 1 S3 186 2o5 210 212 219 221 228 238 256
Control
0-5
4.35
4.0
4.3
4.1
4.80
4.6
4.2
4.5
4.5
4.8
4.7
4.7
5-10
4.7
4.15
4.7
4.4
4.90
5.15
4.5
5.3
-
6.0
5.7
5.3
10-30
4.95
5.2
4.9
5.1
-
-
-
5.4
-
-
5.6
5.3
T-2
0-5
5.4
7.4
8.3
8.3
10.11
10.5
10.0
10.4
10.3
10.2
10.7
10.6
5-10
5.8
6.2
5.9
6.4
10.40
10.4
10.0
9.45
-
8.7
10.6
10.5
10-30
5.6
5.5
6.1
5.65
-
-
-
6.2
-
-
9.2
10.1
T-2
0-5
6.3
5.95
6.7
6.3
6.65
5.9
10.8
11.4
10.8
10.5
11.1
11.0
5-10
6.25
5.7
5.9
6.6
5.70
6.7
9.9
10.55
-
10.1
10.75
10.3
10-30
5.2
5.3
5.3
6.25
8.5
9.3
5.9
-------
TABLE C-4. pH OF CLAY SOILS CORE SEGMENTS - ETHION SPILL
Depth
(cm)
Initial
1
2
9
16
23
30
37
44
52
59
65
Control
0-5
6.4
4.1
4.5
3.75
4.25
4.0
3.85
3.7
5.85
4.1
—
4.7
5-10
6.4
4.3
4.25
3.85
4.35
4.0
4.0
4.4
5.85
4.3
5.0
4.6
10-30
6.3
4.3
4.35
5.55
3.8
4.8
4.45
5.95
5.0
6.4
4.4
5.0
T-2
ho
0-5
*
3.8
4.5
3.7
4.35
3.85
4.1
3.75
7.0
5.4
6.5
6.4
5-10
*
4.1
4.3
4.25
3.9
4.0
5.7
4.1
5.85
4.9
5.3
5.3
10-30
*
4.3
4.5
4.95
4.35
4.25
4.3
4.2
5.7
4.7
5.6
5.2
T-2
0-5
*
4.3
3.85
4.15
4.15
3.9
3.85
3.9
6.45
4.8
5.75
6.0
5-10
*
4.3
4.25
4.45
4.25
3.9
4.0
4.2
4.65
4.1
5.6
4.8
10-30
*
4.3
4.8
5.0
4.65
5.35
4.15
4.2
6.45
4.3
5.5
4.8
(continued)
-------
TABLE C-4 (continued)
Depth
(cm) 72 79 86 93 101 108
Control
0-5
4. 75
4.2
4.9
4.5
3.9
3.4
5-10
4.9
4.65
5.0
4.1
4.0
3.8
10-30
4.95
5.9
5.65
4.5
5.0
4.2
-2
0-5
5.9
6.6
6.4
5.95
6.1
4.7
5-10
5.1
5.25
5.9
4.9
5.9
4.8
10-30
4.75
4.4
6.1
5.4
5.4
5.7
-2
0-5
6.8
6.0
6.5
6.5
6.0
5.5
5-10
5.8
5.0
4.45
5.5
4.6
4.3
10-30
6.0
5.5
4.95
4.9
5.4
4.5
(continued)
113
121
127
136
142
4.45
3.8
3.4
3.2
3.65
4.8
3.5
4.0
2.95
3.7
6.4
4.85
5.0
-
4.7
6.85
6.2
5.2
5.2
4.3
6.45
5.6
5.1
4.5
3.8
5.6
4.9
5.15
4.0
4.65
6.2
5.8
5.25
6.25
5.3
4.65
5.0
4.4
4.4
4.5
5.4
5.4
4.7
4.3
4.8
-------
TABLE C-4 (continued)
Depth
(cm)
155
158
183
186
205
210
212
219
221
228
238
249
256
Control
0-5
3.35
3.55
3.5
3.5
4.10
4.3
4.4
3.85
3.8
4.1
4.3
5.2
4.1
5-10
4.25
3.6
3.5
3.3
3.95
3.8
4.1
4.1
-
4.6
4.45
4.8
4.2
10-30
5.0
4.8
5.4
4.0
-
-
-
4.05
-
-
4.35
5.85
4.75
T-l
0-5
6.5
9.7
9.9
10.0
10.71
10.8
10.9
10.6
10.6 ¦
10.6
10.6
10.2
10.6
5-10
6.2
5.0
9.5
10.0
10.50
10.35
10.5
10.6
-
10.7
10.4
10.3
10.85
10-30
6.15
4.5
6.7
10.2
-
-
-
10.55
-
-
7.85
8.8
10.6
T-2
0-5
5.4
5.5
5.3
6.6
5.80
5.9
10.15
10.7
10.5
10.0
10.9
10.5
10.9
5-10
_
4.0
5.1
5.6
4.40
4.7
9.1
10.6
-
10.3
10.6
10.45
10.8
10-30
_
4. 35
4.65
5.05
-
-
-
10.9
-
-
10.8
10.4
10.7
-------
TABLE C-5 PERCENT MOISTURE IN ORGANIC SOILS - ETHION SPILL
Depth
(cm) Initial 1 2 9 16 23 30 37 44 52 59 65
Control
0-5 9.6 13.27 12.39 9.16 16.26 — 35.84 28.22 6.6 17.10 23.4 14.07
5-10 8.4 7.20 11.68 4.96 11.76 — — — 7.15 18.61 15.1 28.13
10-30 13.3 4.24 15.30 3.20 19.14 20.84 18.54 14.37 9.14 14.68
to T-2
00
° 0-5 * 20.06 14.29 13.94 16.05 36.13 42.12 18.07 20.78 14.58 14.1 15.86
5-10 * 2.87 15.21 17.95 11.19 16.11 6.50 27.59 21.04 5.33 18.7 16.81
10-30 * 5.O8 15.96 14.31 15.85 15.18 — 13.71 14.32 19.58 14.3 9.11
T-2
0-5 * 19.78 22.49 36.49 22.23 17.81 17.62 22.39 15.94 12.04 22.9 25.02
5-10 * 3.77 10.54 18.65 7.83 24.10 22.68 15.37 16.98 29.38 18.5 19.55
10-30 * 4.20 12.81 15.40 14.05 11.33 21.21 15.84 10.97 22.29 15.8 16.25
t + t ~ *
t chambers watered
(continued)
-------
TABLE C-5. (continued)
DopLh Days
(cm) 72 79 86 93 101 108 113 121 127 136 142
Control
0.5 10.25 16.04 8.54 12.94 24.40 15.10 23.24 13.44 28.3 17.0
5-10 5.42 12.67 14.51 14.78 16.92 14.33 16.83 13.13 18.0 16.8 17.4
10-30 24.98 15.09 15.07 15.74 17.71 14.16 19.08 15.59 17.1 16.2 16.4
T-l
0 5 16.11 19.84 - 21.82 19.91 22.47 26.52 14.81 19.72 20.24 24.9
5-1(1 16. 74 22.38 19.77 18.64 22.51 23.53 21.04 19.94 18.4 21.6 20.8
10-30 20.00 15.58 16.05 19.80 20.90 19.71 18.67 27.39 37.8 21.1 20.13
T-2
0-5
22.66 27.09 24.33 26.92 23.82 35.51 23.55 23.89 23.0 30.7
5-10 15.45 18.09 18.35 22.26 18.45 20.15 22.20 20.06 20.2 21.7 20.1
10-30 18.02 20.75 18.22 20.81 16.93 28.34 21.48 20.36 19.2 19.4 19.6
(continued)
t chambers watered
-------
TABLE C-5 (continued)
Depth Days
-------
TABLE C-6. PERCENT MOISTURE IN SANDY SOILS - ETHION SPILL
Depth Days
(cm) Initial 1 2 9 16 21 30 37 44 52 59 65
Control
0-5 7.3 — 7.25 9.84 10.00 10.74 21.95 12.53 17.32 22.92 20.2 14.59
5_10 5.1 8.14 26.86 22.79 1.88 16.75 4.90 9.47 18.93 23.10 18.8
10-30 10.0 7.41 17.04 5.04 15.20 16.42 15.14 15.90 6.07 18.04 17.1 14.16
T-l
0-5 * — 9.38 13.63 9.33 -- 12.44 24.98 9.94 15.82 8.8 16.00
5-10 * 8.11 9.17 11.00 8.05 12.96 10.08 20.83 14.62 17.84 20.3 17.55
10-30 * 5.87 13.78 16.07 8.05 16.23 15.32 12.74 15.87 18.24 19.0 15.60
T-2
0-5 * -- 5.61 12.32 22.61 12.39 15.15 9.38 14.58 16.76 20.1 8.76
5-10 * 13.63 5.63 7.40 — 2.47 13.80 18.44 5.10 9.81 17.2 11.07
10-30 * 10.17 4.18 11.09 20.32 12.25 18.41 13.56 10.12 18.4 20.00 21.71
+ t + + t
+
Assumed same as control
chambers watered
(continued)
-------
TABLE C-6 (continued)
Depth Days
(cm) 72 79 86 93 101 108 113 121 127 136 142
Control
0-5 15.48 17.60 12.78 38.46 17.99 16.80 21.21 13.78 14.7 17.6
5-10 17.37 13.79 18.87 18.75 15.97 19.80 20.26 17.80 16.7 21.8 20.5
10-30 18.66 16.97 14.61 16.17 6.40 18.60 15.40 19.82 18.6 19.44 19.7
T-l
0-5 18.52 14.75 12.76 19 09 14.58 19.50 10.49 22.62 22.8 18.5
5-10 14.93 18.25 18.08 20 12 20.55 13.63 12.24 22.24 22.7 21.0 22.7
10-30 17.71 21.64 19 14 20.51 19.17 20.30 19.16 23.23 18.4 22.1 23.1
T-2
0-5 16.09 20.93 16.45 19.41 20.63 — 16.05 32.32 18.3 19.38
5-10 18.46 18.56 20.43 17.56 19.00 21.59 18.09 28.71 21.4 21.05 21.9
10-30 17.64 19.16 21.44 15 45 24.42 21.00 20.14 16.86 24.6 25.7 22.3
(continued)
* Assumed same as control
f chambers watered
-------
TABLE C-6. (continued)
Depth Days
(cm) 155 158 183 186 205 210 212 219 221 228 238 249
Control
0-5 15.64 — 12.03 15.62 16.31 15.10 14.31 13.51 13.68 10.89 10.03 16.28
5-10 18.56 — 16.36 17.18 18.97 16.50 16.67 — 17.82 13.75 13.64 31.74
10-30 — — 19.06 21.39 — — 19.11 — -- 16.65 17.60 15.79
T-l
0-5 23.92 20.47 18.15 17.18 20.14 20.30 16.28 17.02 19.13 17.20 25.03 10.83
5-10 20.82 22.16 19.35 24.67 22.30 23.93 29.07 -- 25.06 19.98 23.48 19.97
10-30 23.79 23.27 25.00 26.58 — — 24.87 — — 30.06 26.58 24.40
T-2
0-5 19.23 16.39 21.36 18.76 21.30 21.54 23.82 23.57 21.10 21.72 23.63 18.78
5-10 29.27 17.12 22.07 22.17 17.44 24.01 27.45 — 24.57 — 21.99 20.35
10-30 22.43 20.45 24.11 22.89 — — 26.21 — — 23.23 24.99 22.08
* Assumed same as control
+ chambers watered
-------
TABLE C-7. PERCENT MOISTURE IN CLAY SOILS - ETHION SPILL
Depth Da/S
(cm) Initial 1 2 9 16 23 30 37 44 52 59 65
Control
0-5 9.0 — 9.45 7.12 13.70 9.17 15.63 15.05 5.9 13.64 17.0 15.36
5-10 11.7 5.05 16.00 11.45 17.10 16.59 10.10 15.65 8.6 8.88 16.6 13.15
10-30 11.3 4.26 13.76 6.33 17.10 3.77 13.35 9.15 14.33 13.65 13.3 17.00
T-l
0-5 * 13.95 10.60 13.22 9.66 6.67 4.09 7.95 3.7 10.65 12.6 15.84
5-10 * 4.70 3.63 12.08 16.05 19.15 15.94 11.12 13.25 10.61 15.0 9.11
10-30 * 4.99 14.15 11.09 11.87 3.93 8.38 14.17 17.25 13.02 13.8 12.99
T-2
0-5 * 11.01 11.06 — 3.21 15.80 — 22.29 12.5 14.00 15 9 16.56
5-10 * 5.52 7.79 7.84 7.41 14.29 11.13 12.00 15.49 6.29 13.0 13.11
10-30 * 4.58 12.27 13.83 8.76 18.62 — 18.16 10.44 10.88 13.1 12.15
t
Assumed same as control
chambers watered
(continued)
-------
TABLE C-7 (continued)
Depth
(cm)
72
79
86
93
101
Uays
108
113
121
127
136
142
Control
0-5
16.60
14.68
14.59
14.92
13.78
13.60
13.85
17.77
15.7
15.7
—
5-10
15.34
16.21
13.15
14.92
14.20
13.05
14.20
16.48
16.1
16.09
15.5
]H-10
17.14
15.53
24.24
17.53
17.78
14.86
16.47
19.31
16.7
17.5
15.64
'-1
0-5
12.18
10.89
6.68
15.15
11.44
11.51
10.87
21.33
11.3
12.5
5-10
14. 72
17.01
34.91
12.82
15.64
10.54
12.28
15.86
14.0
15.1
12.6
10-30
14.55
18.65
17.74
16.00
16 40
15.08
12.47
35.91
14.4
14.6
13.8
'-2
0-5
14.68
16.82
11.56
13.64
16.27
18.08
14.99
15.59
12.9
18 7
5-10
11.94
10.88
10.62
14.54
13 93
16.35
14.28
17.91
14.2
15.2
18.4
10-30
15. 27
15.28
—
14.89
14.34
17.14
14.79
18 35
15.1
19 4
14.5
^chambers watered
(continued )
-------
TABLE C-7 (continued)
Depth
Days
(era) 155 158 183 186 205 210 212 219 221 228 238 249
Control
0-5 14.29 13.22 24.28 13.73 16.00 17.43 15.63 15.42 16.64 14.00 13.50 12.71
5-10 17.00 13.10 15.79 16.39 18.11 18.90 15.14 — 16.64 13.81 14.08 12.67
10-30 16.19 19.92 16.54 15.67 — — 14.83 -- — 13.62 15.49 14.96
T-l
0-5 — 30.33 12.02 13.74 15.91 15.33 11.36 17.13 15.24 8.41 10.60 11.47
5-10 — 26.75 15.79 21.89 15.52 15.74 24.70 — 16.90 12.85 12.95 13.33
10-30 -- 29.24 11.24 21.20 — — 17.76 — — 15.08 12.86 14.39
T-2
0-5 19.35 15.70 25.43 12.89 16.13 16.13 17.33 18.14 16.36 13.73 21 63 9.89
5-10 16.70 13.34 5.79 7.85 16.72 16.81 17.76 — 17.27 12.81 14.04 11.93
10-30 16.31 15.53 16.05 14.93 — — 17.02 -- — 18.26 14.29 14.36
+ chambers watered
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
<
a:
o
cc 1
£10,000,000--
tn
cz. —
LU
tn
© CONTROL
i-
<
A T-2
100,000 --
60 70
DAYS
160
225
Figure C-1. Middle level organic soil bacterial populations - Ethion spill.
-------
A. T—1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
100,000,000 ~j—|—i—|—i—|—i—|—i—|—i—|—i—|—i—|—i—|—i—|—i—|—i -|—i—p
2 10,000,000
o
oc
ID
Q_
(/)
a:
UJ
CD
s:
3
z
CO
1,000,000 —
100,000--
O CONTROL
0 T-1
A T-2
1T I I | | | | I I I I ! I I !_| |_| I I j I
n 15 25 35 41 C5 65 75 85 9
J
-5 15 15 25 35 ^55 65 75 85 9^ 1051 121S
A B C DAYS D E F F F
Figure C-2. Lower level organic soil bacterial population - Ethion spill.
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
s:
Qd
O
CX.
LU
Q_
£ 1,000,000
LU
CD
£
3
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<
H
100,000
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o
-------
A.
B.
C.
T-1 AND T~2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
100,000,000
10,000,000--
V)
DC
UJ
OQ
E
3
Z
© CONTROL
~ T-1
A T-2
1,000,000--
«£
t-l
ILI
I-
u
¦t
m
-ri
DAYS
A
B C D
D
E F F F
Figure C-4. Lower level sandy soil bacterial population - Ethion spill.
-------
A.
B.
C.
T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED
T-1 AND T-2, LIMED, T-2 PLOWED
T-1 AND T-2, LIMED AND NUTRIENT BROTH
D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
E. T-1 AND T-2, ETHANOL-WATER SOLUTION
F. T-2, ETHANOL-NaOH SOLUTION
100,000,000
10,000,000 --
1,000,000
UJ
m
s:
3
z
O CONTROL
~ T-1
<
i—i
100,000
a:
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l-
AT-2
u
<
m
10,000 --
65 75
1051155
205'
225
B C
A
D
E
F FF
DAYS
Figure C-5. Middle Level clay soil bacterial populations - Ethion spill.
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED
B- T-1 AND T-2, LIMED, T~2 PLOWED
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH
D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
E. T-1 AND T-2, ETHANOL- WATER SOLUTION
F. T-2, ETHANOL-NaOH SOLUTION
10,000,000 --
on
UJ
Q_
UJ
O CONTROL
CD
s:
<
A T-2
100,000 --
UJ
I—
•x
CD
10,000 __
E F F F
D
B C
A
DAYS
Figure C-6. Lower level clay soil bacterial populations - Ethion spill.
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
© CONTROL
a T-1
A T-2
UJ
I—
3
Z
£
300
UJ
OL
200
CO
I- 100
UJ
Z
170
190
230 250
130 150
60 70 SO 901100
DAYS
Figure C-7. Carbon-14 levels in upper level organic soil - Ethion spill.
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T~1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
© CONTROL
0 T-1
A t-2
DAYS
Figure C~8. Carbon-14 Level in upper level - sandy soil - Ethion spill.
-------
A. T-1 AND T-2, NUTRIENT BROTH, T-2 PLOWED D. T-1 AND T-2, NUTRIENT BROTH AND TWEEN 80
B. T-1 AND T-2, LIMED, T-2 PLOWED E. T-1 AND T-2, ETHANOL-WATER SOLUTION
C. T-1 AND T-2, LIMED AND NUTRIENT BROTH F. T-2, ETHANOL-NaOH SOLUTION
© CONTROL
0 T-1
A T-2
Figure C-9. Carbon-14 level in upper level - clay soils - Ethion spill.
-------
APPENDIX D
FORMALDEHYDE DATA
This Appendix contains additional supplemental data obtained on land
restoration techniques for the formaldehyde spill The following data are
included in this Appendix.
•background soil analyses
• pH of soils as a function of core depth and time
•percent moisture of soils as a function of core
depth and time
•formaldehyde levels in the middle and lower soil
layers
•microbial levels in the middle and lower soil
layers
•radiometric data in the upper soil layers
298
-------
TABLE D-l. BACKGROUND ANALYSES OF SOILS - FORMALDEHYDE SPILL
Depth High Organic
Property Meaasure (cm) Soil Sandy-Loam Clay Soil
pH 0-5 7.1 5.7 5.A
5-10 6.9 6.0 6.5
10-30 6.8 5.9 6.2
X Moisture 0-5 21.5 9.6 11.7
5-10 15.4 1.5 13.8
10-30 16.2 16.6 14.2
% Organic Matter 0-5 11.8 6.6 6.0
5-10 6.0 6.7 5.5
10-30 5.8 7.0 5.3
Nitrate N (ppm) 0-5 7.0 5 7.5
5-10 7.0 A.5 8.0
10-30 3.0 6.0 8.0
Organic Phosphorus (ppm) 0-5 1«0 0.1 12
5-10 7.5 0.1 7.5
10-30 3.0 10.5 0.1
Total Phosphorus (ppm) 0-5 60 13 19
Potassium (ppm) 0-5 55 139 45
Calcium (ppm) 0-5 624 1200 708
Magnesium (ppm) 0-5 57 120 107
-------
TABLE D-2 pH OF ORGANIC SOIL CORE SEGMENTS " FORMALDEHYDE SPILL
Depth
(cm)
0
1
2
4
5
7
9
11
15
Days
18
22
25
28
32
36
42
49
56
66
ConcroI
0-5
7.1
8.0
9.5
8 0
6.3
5.9
6.0
5.6
5. 7
6.1
5.9
6.2
6 2
5.7
6.2
5.7
6.2
5.2
5.6
5-10
6.9
7.9
a. 7
7. 7
5.6
5.7
5 3
5.2
5.4
5.5
5.4
6.1
5.8
5. 7
5.5
5.9
6.1
5.1
5 5
10-30
6.8
7 7
8.5
6.9
5.8
5.7
5.3
5.0
5.1
5.6
5.4
5.5
5.8
5 4
5.8
4.7
6 0
4.7
5.3
T-l
*
0-5
*
7.8
7.5
7 8
6.0
6.0
5.9
4.4
5.5
5.4
5.5
5.9
5.4
5.4
5.4
5.6
5.4
5.9
6.3
5-10
*
7 3
7.3
6.7
5.7
5.8
5.7
5.1
5.5
5.1
4.8
4.4
5 8
4.9
5. 3
5.7
5.0
5.3
5.2
10-30
*
7.1
7.1
6.4
5.7
5.3
5.8
4.7
5.2
5.5
5.8
5.4
5.3
4.7
4.7
4.6
4.8
4.3
4.4
T-2
0-5
*
8 9
8.9
7.6
6.0
5.9
5.8
5.8
5.5
5 7
5.8
5.7
6.4
5.7
5.6
5.B
6.5
6.1
6.4
5-10
*
7.3
7.3
7.9
5.6
5.6
5.5
5.3
4.9
5.7
5.4
5.6
5.0
5.3
5.0
5 6
5.7
5.3
5.6
10-30
*
7 9
7.9
7.9
5.7
5.7
5.8
5.3
5.2
5.5
5.6
5.7
5.2
5.2
5.5
5.4
5.4
4.7
5.5
* Assumed to be similar to control
Lime added on day 52 and 64 to T-l and T-2.
-------
TABLE D-3. pll OF SANDY SOIL CORE SEGMENTS - FORMALDEHYDE SPILL
Depth
(cm)
0
1
2
4
5
7
9
11
Days
15 18
22
25
28
32
36
42
49
56
66
Control
0-2
6 0
7.3
6.7
7.8
4 8
4.8
5.1
4 5
4.5
4 8
4. 7
4.9
4.7
4.7
4 7
4 4
4.8
4.0
4.9
2-4
5.9
6.3
6.5
7 0
5.0
5.6
5.1
5.0
4.6
5.9
4.7
4.9
5 0
4.6
4.8
4.6
4.8
4.1
4.3
4-12
7.1
6 5
6.3
7.3
5.5
6.2
5.6
5.0
5 8
5.4
5.4
5.9
5.5
4.5
5.5
6.1
5.4
5.3
5.4
T-l
0-2
*
7.0
7.1
6.6
4 9
4 7
5.0
4.7
4.9
5.5
4.7
4.9
5.2
4.6
5.3
4.8
5.5
5.3
6.0
2-4
*
6.8
7.3
6.2
4.9
4 8
5.4
5.0
5.1
5 1
4.8
4.9
5.3
5.1
5.8
4.7
5.3
4.8
5.6
4-12
*
7 3
7.0
6.7
5.9
5.8
5.8
5 6
5.8
5.6
5.7
5 8
5 8
4.8
6.2
4.9
5.4
5.1
5.2
T-2
4.7
0-2
*
7.6
7 9
6.3
5.1
4 5
4.9
4 8
4.7
4.6
4.5
5.0
4.7
4.3
4.7
4.3
4.6
5.4
6.0
2-4
*
7.3
7 6
6 6
5.2
5.2
5.0
4.5
4.8
4.6
4.8
5.0
5.0
4.3
5.8
4.5
4.4
4.8
5.8
4-12
*
7 3
7 3
7 1
5.9
5.1
5.9
4 8
5.3
5.2
5 5
5.6
5.1
4.3
4 9
5.5
5 2
5.4
5.7
* Assumed to be similar to control
Lime added on day 52 and 64 to T-l and T-2.
-------
TABLE D-4. pH OF CLAY SOIL CORE SEGMENTS - FORMALDEHYDE SPILL
Depth
(cm)
0
1
2
4
5
7
9
11
15
Days
18
22
25
28
32
36
42
49
56
66
lontrol
0.5
5 4
6 8
6.7
5.3
4 8
5.2
4.7
4.4
4.6
4.8
5.6
5.0
4.7
4.4
4.5
4.4
4.6
4.2
4.1
5-10
6.5
6.8
6.6
5.5
5.1
5.5
5.3
5 0
4.7
5.3
4.9
5.9
4.9
4.8
5.8
5.0
5.4
5.0
5.0
10-30
6.2.
6.7
6.2
5.2
5.3
5.8
5.3
4.7
5.0
6 0
4.9
5.2
6.1
5.3
4.2
6.0
5.2
5.4
4.6
T-l
0.5
*
6 2
7.3
6.7
4.9
4.9
4.8
4.7
4.3
4.4
4.8
4.9
4.7
4.6
4.5
4.5
4.6
5.5
5.5
5-10
*
5.8
7.2
5.5
4.7
5.7
5.3
5 0
4.6
5.3
5 3
5.0
5.1
4 9
5.3
4.6
5.3
4.8
4.7
10-30
*
5.8
7.2
6.1
5.2
5 7
5.3
5.0
4 8
5.7
5.4
5.1
5.7
4.6
5.2
4.7
6.0
5.2
5.3
T-2
0-5
*
6 5
6 8
5.9
4 8
4.9
4.8
4.6
4 5
4.7
4.7
4.9
4.7
4.9
5 3
5.1
5.3
6.1
5.1
5-10
*
6 5
6 9
5 4
5. 7
5 4
5 0
4.8
4 8
4.9
4.8
4.8
4.8
5.0
4.6
6.1
5 4
4.9
5.6
10-30
*
6.0
7 1
6. J
5 3
5 6
6.0
5.4
4 8
5.4
5.4
5.4
4.9
4.8
5.1
6.0
5.4
5.9
5.8
* Assumed to be similar to control
Lime added on day 52 and 64 to T-l and T-2
-------
TABLE D-5 PERCENT ORGANIC SOIL MOISTURE CONTENT - FORMALDEHYDE SPILL
Depcli Days
(cm) 0 1 2 4 5 7 - 9 11 15 18 22 25 28 32 36 42 49 56 66
Control
0-5 21.5 23.5 30.1 26.2 25.8 - 26.1 23.3 22.5 18.6 24.7 24.8 22.5 - 29 28.9 24.6 28.8 27.4
5-10 15.4 19.1 20.7 19.1 18.7 - 24.6 19.7 21.8 21.6 21.4 21.5 18.3 - 28.2 20.5 22.1 20.8 23.1
10-30 16.2 16.1 13.6 16.3 - - 20.3 18.1 21.3 18.5 20.2 18.6 16.3 - 17.9 19.5 20.7 19.4 22.8
T-l
u>
° 0-5
to
* 22.7 24.6 29.2 30.1 24.5 25.3 28.3 28.7 22.4 18.9 27.1 23.7 29.0 26.1 27.5 23.8 26.2 37.6
5-10 * 21.9 20.5 21.1 21.0 22.7 20 17.2 26.4 19.3 23.9 21.1 23.8 19.3 20.9 23.1 21.3 21.5 21.7
10-30 * 19.8 19.7 19.3 23.9 19.0 18 20.1 19.5 19.6 27.1 20.9 22 21.6 12.8 19.9 21.9 23.4 22.8
T-2
0-5 * 21.0 24.0 21.8 16.8 22.8 16.4 16 15.1 33.8 24.1 23.8 24.1 16.5 28 18.7 19.8 31.6 23 8
5-10 * 9.0 17.0 15.0 13.3 18.0 14.6 18.1 19.1 13.7 19.9 17.7 18.2 15 17.1 16.3 17.9 18.5 22.6
10-30 * 14.1 15.5 7.2 15.9 17.7 15.3 13.7 17.2 15.9 20.3 17.9 19.4 19.6 17.8 16.2 19.3 17.2 20.6
* Assumed to be similar to control
All chambers watered after sampling on day 18, 21 and 49
-------
TABLE D-6. PERCENT SANDY-LOAM SOIL MOISTURE CONTENT - FORMALDEHYDE SPILL
Depth Days
0 1 2 4 5 7 9 11 15 18 22 25 28 32 36 42 49 56 66
Control
0-5 9.6 17.3 18.4 14.4 16.4 - 15.9 11.7 20.7 8.9 14.6 13.7 13.3 19.2 - 12.2 13.9 36.1 19
5-10 1.5 12.3 5.7 17.4 15.8 - 17.8 14.4 6.7 8.3 20.1 15.4 11.0 16.5 13.2 13.9 15.0 15.4 19.3
10-30 16.6 12.5 13.4 14.5 17.9 - 23.7 11.8 16.6 11.3 15.6 19.1 10.9 18.3 11.9 14.3 18.2 19.3 25.2
T-l
0-5 * 21.6 21.0 21.6 18.3 20.8 21.0 21.6 - 15.3 19.0 19.8 22.2 19.3 19.J 17.3 20.8 22.8 22.9
° 5-10 * 15.6 21.2 22.8 19.5 13.5 14.8 21.9 20 17.0 19.7 19.9 19.2 26.9 23.0 18.8 21.6 21.9 21.5
10-30 * 23.7 22.4 25.7 21.9 21.5 21.8 22 20.3 20.3 24.8 22 19.4 21.4 24.9 20.7 23.5 26.5 -
T-2
0-5 * 14.6 11.7 18.2 4.3 15.3 16.6 12.5 9.3 11.7 17.8 15.6 13.3 11.7 4.6 8.2 12.2 15.9 20.1
5-10 * 15.5 5.9 11.4 36.6 14.8 14.4 17.9 11.3 12.3 18.7 17.2 17.0 16.6 19.4 9.5 17.7 18.7 23.4
10-30 * 12.5 13.4 21.1 15.1 17.2 18.9 17.7 16.7 11.5 20.7 19.5 20.2 17.2 11.5 20.3 21.0 22.6 26.1
* Assumed to be similar to control
All chambers watered after sampling on day 18, 21 and 49
-------
TABLE D-7 PERCENT CLAY SOIL MOISTURE CONTENT - FORMALDEHYDE SPILL
Depth Days
(era) 0 1 2 4 5 7 9 11 15 18 22 25 28 32 36 42 49 56 66
Control
0-5 11.7 20.8 16.0 16.4 16.6 14.8 30.5 20 15.2 14.1 15.2 22.6 15.2 14.3 21.1 18.9 14.9 8.2 17.3
5-10 13.8 14 3 - 16.4 11.8 6.7 16 14.6 14.3 15.3 17.1 14.1 16.9 16.3 16.5 14.8 15.7 16.1 18.9
10-30 14.2 13.5 16.6 17.9 14.9 15.3 16.4 15.2 17.8 17.8 16.9 20.3 18.6 17.2 18.7 16.4 16.3 31.4 17
T-l
0-5 * 14.0 12.1 16.2 15.3 16.3 22.7 15.6 14.5 14.5 14.3 14.7 14.7 15.5 13.5 11.9 14.7 16.7 21.4
5-10 * 13.4 9.3 13.7 13.4 16.9 17.1 16.8 14.4 20.1 16.4 14.5 17.0 15.4 17.2 12.8 15.9 12.8 20.1
10-30 * 20 15.2 18.1 18.0 16.8 13.8 13.9 13.5 17.4 19.8 17.5 16.7 17 20.4 16.5 18.1 16.4 18.5
T-2
0-5 * 15.5 13.8 16.7 12.1 10.7 14.4 11.5 12.0 9.7 14.7 13.6 17.0 12.3 16.6 14.5 12.5 18.6 17.7
5-10 * 10.1 13.3 16.3 15.8 14.1 13.8 16.1 19.1 11.4 13.9 14.4 15.5 20.7 9.0 9.1 13.4 13.4 8.7
10-10 * 8.6 6.1 15.5 13.6 10.9 14.0 11.1 13.9 13.5 16.9 15.8 16.5 16 17.8 14.6 14.8 14.5 19.8
* Assumed to be similar to control
All chambers watered after sampling on day 18, 21 and 49
-------
8,000
1,000-
O CONTROL
~ T-1
A T-2
A. T-1, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT
CULTERED WITH
5000 PPM
FORMALDEHYDE
B. T-1 , T-2, LIME ADDED
Figure D-1. Formaldehyde Levels - rrnddle soil layer (5-10 cm) - organic soil.
306
-------
7,000
1,000 —
x
>-
0£
O
CL
Q.
>
UJ
>-
n
<
a:
o
0 CONTROL
A. T-I, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT
CULTERED WITH
5000 PPM
FORMALDEHYDE
B. T-l, T-2, LIME ADDED
100
40
DAYS
Figure D-2. Formaldehyde levels - lower soil layer (10-30 cm) - organic soil.
307
-------
10,000
X1,000
>-
oc
o
Q.
a.
LU
>
a
-------
O CONTROL
~ >1
AT-2
PRIMARY SEWAGE EFFLUENT
PRIMARY SEWAGE EFFLUENT
CULTERED WITH 5000 PPM
FORMALDEHYDE
T-l, T-2, LIME ADDED
Figure D-4. Formaldehyde Levels - lower soil layer (10-30 cm) - sandy soil.
309
-------
2,000
1,000 -
x
o
UJ
3
a:
o
a
o.
UJ
>
a
>-
x
<
£
01
o
100 —
10
0 CONTROL
~ T-1
A T-2
PRIMARY SEWAGE
EFFLUENT
PRIMARY SEWAGE
EFFLUENT
CULTERED WITH
5000 PPM
FORMALDEHYDE
1, T-2, LIME ADDED
Figure 0-5. Formaldehyde Levels - middle soil layer (5~10 cm) - clay soil.
310
-------
1,000
>-
a:
o
o.
cl
>
LU
UJ
a
>
-j
<
q:
o
100 —
10
0 CONTROL
PRIMARY SEWAGE EFFLUENT
2, PRIMARY SEWAGE EFFLUENT
CULTERED WITH 5000 PPM
FORMALDEHYDE
T-2, LIME ADDED
Figure D-6. Formaldehyde levels - lower sot I layer (10-30 cm) - clay soil.
311
-------
30,000,000
A. T-l, PRIMARY SEWAGE EFFLUENT
T-2, PRIMARY SEWAGE A
EFFLUENT CULTURED
WITH 5000 PPMr-i
FORMALDEHYDE r1 ^ /
BACTERI
© CONTROL
~ T-1
A T-2
1,000,000
UJ
Q.
CO
UJ
CO
00,000
_i
<
>—i
CO
o
a:
o
FUNGI
10,000
l
DAYS
Figure D-7. Middle Level organic soil microbial population - formaldehyde spill.
312
-------
30,000,000
A. T-l, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT CULTURED
WITH 5000 PPM
FORMALDEHYDE J
10,000,000
©CONTROL
QT-1
A T-2
1,000,000
ce
ej
a:
CD
FUNGI
100,000
10,000
-5 Of 5 10 15 20 25 30 35 AO 45
A DAYS '
Figure D-8. Lower level organic soil microbial population - formaldehyde spill.
313
-------
T-l, PRIMARY SEWAGE EFFLUENT
T-2, PRIMARY SEWAGE EFFLUENT
CULTURED WITH 5000 PPM
FORMALDEHYDE
BACTERI/
O CONTROL
~ T-1
A T-2
FUNGI
m
100,000
10,000
1
-5 Of 5 10 15 20 25 30 35 40 45
A DAYS |
Figure D-9. Middle Level sandy soil microbial population - formaldehyde spill.
314
-------
100,000,000
10,000,000
SL
<.
a.
o
cc
UJ
a.
CO
on
UJ
m
s:
3
00
o
ac
1,000,000
100,000
-i 1 1 1 r
T-l, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT CULTURED WITH
5000 PPM FORMALDEHYDE
10,000
0 CONTROL
~ T-1
AT-2
BACTERIA
FUNGI
1 1 1 1 1
I I I
5
°i
5
10 15 20 i
DAYS
£ 30 35 40 45
Figure D-10. Lower Level sandy soil microbial population - formaldehyde spill.
315
-------
7,000,000
. A.
1,000,000
<
ce
is
oo
ce.
CD
£
m
o
o:
100,000
10,000
1 r
T-l, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT CULTURED WITH,
5000 PPM FORMALDEHYDE/
0 CONTROL
~ T-1
A T-2
10 15 20 25 30 35 40 45
BACTERIA
FUNGI
Figure D—11. Middle level clay soil microbial population - formaldehyde spill.
316
-------
10,000,000
1,000,000
<
cc.
o
cc
LU
Q.
UJ
m
r>
z
m
o
ce
100,000
10,000
-i 1 1 1 i i i r
0 CONTROL
~ T-1
A T-2
-1, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT CULTURED
WITH 5000 PPM
FORMALDEHYDE ~
BACTERIA
FUNGI
_L
I
_1_
-5
10 15 20
DAYS
25 30 35 AO 45
Figure D-12. Lower Level clay soil microbial level population
formaldehyde spill.
317
-------
a.
GO
ID
O
300
250
200 -
150 -
PRIMARY SEWAGE EFFLUENT
PRIMARY SEWAGE EFFLUENT
CULTERED WITH 5000 PPM _
FORMALDEHYDE
T-l, T-2, LIME ADDED
CONTROL
DAYS
100 -
Figure 0-13. Radiation counts in upper layer of organic soils - formaldehyde spill.
-------
200
cc.
UJ
O-
3
o
150 -<
100
50 --
1—
O CONTROL
~ T-1
A T-2
I I
A. T-1, PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT CULTURED
WITH 5000 PPM
FORMALDEHYDE
B. T-1, T-2, LIME ADDED
60 I
A A DAYS B B
Figure 0-14. Radiation counts in upper layer of sandy soils - formaldehyde spill.
-------
OJ
to
o
100 --
80 -
60 __
AO
20
A. T-l , PRIMARY SEWAGE
EFFLUENT
T-2, PRIMARY SEWAGE
EFFLUENT
CULTERED WITH
5000 PPM
FORMALDEHYDE
B. T-l , T-2, LIME ADDED
© CONTROL
~ T-l
A T-2
20 f 30 40
A DAYS
Figure D-15. Radiation counts in upper level of clay soils - formaldehyde spill.
-------
APPENDIX E
ANILINE DATA
This appendix contains additional supplemental data obtained on land
restoration techniques for the aniline spill. The following data are included in
this Appendix.
•background soil analyses
• pH of soil as a function of core depth
and time
•percent moisture of soils as a function of
core depth and time
•Aniline concentration - middle soil layers
321
-------
TABLE E-l. BACKGROUND
ANALYSES OF SOILS
- ANILINE SPILL
Property
Depth
Organic
Sandy-loam
Clay
Measured
(cm)
Soil
Soil
Soil
plf
0-5
7.5
6.6
5.1
5-10
6.2
6.4
5.8
10-30
6.2
6.7
5.5
% Moisture
0-5
24.3
18.2
15.7
5-10
22.A
19.1
26.0
10-30
27.6
22.8
12.7
2 Organic Matter
0-5
15.7
2.0
2.0
5-10
5.9
2.9
0.9
10-30
9.0
2.9
1.0
Nitrate N (ppm)
0-5
5
10
1Z
5-10
17
7
6
10-30
10
10
0
Total Phosphorus
(ppm) 0-5
60
13
19
Potassium (ppm)
0-5
55
139
45
Calcium (ppm)
0-5
624
1200
708
Magnesium (ppm)
0-5
57
120
107
-------
TABLE E-2. pH OF ORGANIC SOILS - ANILINE SPILL
ro
Depth
(cm)
Control
0-5
5-10
10-30
T-l
0-5
5-10
10-30
T-2
0-5
5-10
10-30
Pre-Anlllne
Sample
-2 1
7.5
6.15
6.2
Days
16
15
17
34
7.0
6.3
5.15
7.15
5.4
A.8
7.2
5.0
5.4
6. 55
6.25
6.25
6.55
5.8
5.6
6.05
4.8
5.25
4.7
5.7
7.2
7.45
6.5
5 8
7.15
5.7
5.4
7.1
5.55
5.7
7.5
7.5
7.1
7.4
7.45
6.1
7.1
6.7
6.6
7.5
6.7
7.8
6.0
6.4
6.2
37
7.3
7.25
6.8
43
50
7.15
7.1
6.4
7.15
7.1
6.3
57
7. J
7.3
6.1
~assumed same as control
(continued)
-------
TABLE E-2. (continued)
Depth Days
71 77 84 91 100 105 113 124 133 141 152 159 166
Control " " """" "
0-5 ?.2 7-2 77-3 7.35 7.5 7.1 7.5 6.2 7.25 7.35 7.4 7.25
5-10 7.0 6.75 6.8 6.35 6.8 6.2 6.9 7.5 7.3 6.3 7.25 6.0 7.3
10-30
T-l
0-5 7-3 7.1 8.4 7.6 7.2 7.5 7.4 7.6 7.3 7.4 7.3 7.4 7.4
5-10 7.0 5.9 6.8 6.9 6.9 6.9 6.4 7.6 6.6 6.6 6.2 6.3 7.3
10-30
T-2
0-5 6-2 6-4 6.9 5.1 6.8 6.5 6.3 6.45 6.6 6.8 6.6 7.3 6.6
5-10 6.6 6.8 7.0 6.0 5.8 6.8 7.0 7.7 6.8 6.95 7.4 7.1 7.35
10-30 -
(continued)
-------
TABLE E-2. (continued)
Depth
(cm)
174
181
Days
Control
0-5
7.2
7.3
5-10
7.0
5.5
10-30
-
-
T-l
0-5
7.3
7.1
5-10
6.6
5.3
T-2
0-5
7.0
7.1
5-10
7.2
7.A
10-30
-------
TABLE E-3 pH OF SANDY SOILS - ANILINE SPILL
Deptli
(cm)
Control
0-5
5-10
10-30
T-l
0-5
5-10
10-30
T-2
0-5
5-10
10-30
Pre-Anlllne
Sample
-2 1
6.1
5.8
5.5
7.05
6.55
6.25
6.45
5.8
5.6
7.1
5.1
6.15
6.95
6.5
5.55
6.5
6.1
5.85
7.05
6.65
5.0
4.0
6.3
7.5
Days
14
15
17
34
37
43
50
7.1
6.0
5.85
6.6
6.3
6.15
6.3
6.7
7.1
7.2
6.7
6.6
7.2
6.8
5.9
6.9
6.4
6.4
7.0
6.9
6.8
6.7
6.6
6.6
7.1
6.65
6.2
6.9
6.5
5.9
6.9
6.3
5.5
57
7.1
6.7
5.8
*assumed same as control
(continued)
-------
Depth
(cm) 71 77 84 91
Control
0-5 7.1 6.95 8.7 7 4
5-10 7 4 6.8 8.0 7.4
10-30 -
T-l
0-5 6.6 6.35 6.7 6.4
5-10 6.4 6.2 6.6 6.45
10-30 -
T-2
0-5 6. 2 6.2 7. 1 5.3
5-10 6.45 6 7 8.2 6.1
10-30 -
TABLE E-3 (continued)
100
Days
105 113
124
133
141
152
159
166
7.5
7.1
7.3
6.9
7.0
6.45
7.0
6.6
7.1
7.1
7.5
7.65
7.6
7.4
7.6
7.8
7.55
7.2
6.6
6.7
6.6
6.7
6.3
6.7
6.2
6.85
7.0
6.0
6.5
6.2
6.5
7.2
7.25
7.4
7.1
7.6
6.8
7.5
5.0
5.6
5.5
6.6
6.5
6.7
7.3
7.5
6.9
8.0
7.6
6.7
7.9
8.0
8.1
8.2
(continued)
-------
TABLE E-3 (continued)
Depth Days
(cm) 174 181
Control
0-5 7.5 7.6
5-10 7.4 6.9
10-30
T-l
0-5 7.9 6.9
5-10 6.7 7.2
10-30
T-2
0-5 8.2 7.4
5-10 8.0 7.5
10-30
-------
TABLE E-4. pH OF CLAY SOILS
Pre-Anlllne
Depth Sample Days
(cm) -2 1 2 5 7 14 15
Control
0-5 6.6 6.4 6.15 3.2 10.0 10 0 9.2
5-10 6.4 5. 75 5.45 - 5.5 - -
10-30 6.7 5.2 6.7 - 5 15
T-l
0-5 * 6.1 5.7 9.6 5.65 5.8 6.0
5-10 * 5.6 5.8 - 5.7 -
to
^ 10-30 * 5. 2 5.7 5.9
T-2
0-5 * 6.65 5.9 4.2 6.7 5.8 5.8
5-10 * 5.3 5.7 - 6.15
10-30 * 5.5 6.1 - 5.1
^assumed same as control
(continued)
ANILINE SPILL
17 34 37 43 50 57
8.1 7.1 7.2 7.0 6.85 6.9
- 6.8 - -
5.5
5.9
5.9
5.5 5.65 5.5 5.75
5.7
7.5
6.4
6.7 5.2 6.0 6 4
-------
TABLE E-4. (continued)
Depth —Days
(cm) 71 77 84 91 100 105 113 124 133 141 152 159 166
T-l
0-5
5-10
10-10
T-2
0-5
Control
0-5 7.7 7.8 10.9 9.9 9.7 10.5 6.65 9.4 10.4 7.5 7.4 6.7 10.1
5-10 6.4 6.4 8.3 8.5 6.3 9.8 5.6 9.3 8.7 7.0 5.6 6.4 8.6
10-30 - -- -- -- -- -- --
5.7 5.6 7.1 6.3 6.0 5.6 5.5 5.6 6.0 5.9 5.7 7.6 6.2
5.75 5.7 6.9 6.2 5.4 6.3 5.6 6.15 5.6 5.9 6.1 6.25 5.6
6.55 6.3 6.3 6.3 6.9 6.95 7.3 7.25 6.9 7.2 6.5 7.5 6.7
5_10 5.0 6.85 5.4 5.95 6.6 6.95 6.2 6.95 6.7 7.5 6.7 7.2 5.4
(continued)
-------
Depth
(cm) 174 181
Control
0-5 9.4 10.1
5-10 7.6 8.6
10-30
1-1
0-5 6.5 7.0
5-10 6.65
10-30
T-2
0-5 7.6 6.9
5-10 6.7 7.7
10-30
TABLE E-4. (continued)
Days
-------
TABLE E-5. PERCENT MOISTURE IN ORGANIC SOILS - ANILINE SPILL
Depth
(cm)
Control
0-5
5-10
10-30
T-l
0-5
5-10
10-30
T-2
0-5
5-10
10-30
Pre-Aniline
Sample
-2
Days
7 14
15
34
37
43
50
57
71
24.27
22.42
27.62
26.65
25.10
20.71
29.56
22.88
19.68
41.04
20.48
18.45
25.15
28.48
21.41
29.61
20.18
22.88
27.95
18.45
21.32
28.86
24.95
35.69
27.14
20.03
20.99
22.03
11.01
9.0
33.86
8.23
8.07
37.02 39.61
42.66 44.17
37.52 38.56
34.69
19.06
37.77
25.38
35.36
23.45
41.18 33.59 24.0 29,36
33.94 30.06 31.61 30.21
32.02 34.59 35.03 34.57
27.27
21.
33.
30.
33.
17.
^assumed same as control
(continued)
-------
TABLE E-5. (continued)
Depth Days
-------
TABLE E-5. (continued)
Depth Days
(cm) 174 181
Control
0-5 33.00 26.48
5-10 23.10 20.68
10-30
T-l
0-5 34.34 31.07
5-10 29.96 23.02
10-30
T-2
0-5 47.82 23.80
5-10 53.93 34.69
10-30
-------
TABLE E-6 PERCENT MOISTURE IN SANDY SOILS - ANILINE SPILL
Pre-Aniline
Depth Sample Days
"2 1 2 5 7 14 15 34 37 43
50 57 71
Control
0-5 18.23 28.60 26.72 25.18 8.38 25.36 25.09 25.65 24.33 24.02 25.25 23.15
5-10 19.12 26.29 25.69 - 6.54 - - 23.68 -
10-30 22.81 26.52 25.99 - 8.46
T-l
0-5 * 22.78 24.29 22.00 5.71 24.98 24.12 23.61 22.79 31.03 25.62 22.27
5-10 * 19.01 21.84 - 6.02 - - 20.75 -
1^-30 * 21.84 21.34 - 7.11
T-2
0-5 * 23.29 27.04 20.69 6.73 23.14 29.74 26.50 26.80 28.07 25.33 26.27 27.65
5"10 * 20.00 - - 6.13 - - 23.65 - 18.62
10-30 * 27.05 23.48 - 9.5 -
22.50
22.63
34.78
18.32
*as8umed same as control
(continued)
-------
TABLE E-6 (continued)
Depth "Bays
(cm) 77 84 91 100 105 113 124
Control
0-5 21.86 19.27 23.75 23.36 21.67 20.89 21.19
5-10 21.38 41.10 6.64 20.21 20.27 21.04 20.33
10-30 _______
T—1
0-5 21.80 18.96 20.80 20.13 26.35 19.93 22.31
5-10 18.34 19.20 18.13 19.55 21.03 19.91 28.66
10-30 _______
T-2
0-5 26.36 22.77 21.45 24.75 22.58 24.53 25.98
5-10 21.24 21.25 19.35 20.70 16.43 22.17 18.18
10-30 _______
(continued)
133 141 152 159 166
21.33
23.81
21.12
17.42
20.79
21.83
19.69
21.37
21.93
23.23
19.22
19.16
22.96
19.77
20.68
20.00
25.05
20.74
23.34
21.25
27.78
20.23
16.94
21.58
21.12
21.21
21.64
21.50
21.09
-------
TABLE E-6
(continued)
Depth _
(cm) 174 181 ays
Control
0-5 23.59 18.41
5-10 16.86 28.81
10-30
T-l
0-5 26.97 20.59
5-10 22.38 22.67
10-30
T-2
0-5 21.92 23.66
5-10 22.46 23.95
10-30
-------
TABLE E-7. PERCENT MOISTURE IN CLAY SOILS - ANILINE SPILL
Depth
(cm)
Pre-Aniline
Sample
-2 1
2
5
7
Days
14
15
34
37
43
50
57
71
Control
0-5
15.74
10.64
17.85
18.73
9.48
18.13
21.21
13.64
13.86
17.32
17.80
24.21
13.96
5-10
26.01
16.74
16.92
-
7.56
-
-
16.75
-
-
-
-
14.88
10-30
12. 70
18.32
24.21
-
10.99
-
-
-
-
-
-
-
-
T-l
0-5
A
18.44
28.52
15.83
5.23
15.04
15.38
15.63
13.83
20.0
17.53
16.35
11.67
5-10
*
18.16
17.36
-
10.15
-
-
15.83
-
-
-
-
12.22
10-30
*
18.08
17.73
-
4.87
-
-
-
-
-
-
-
-
r-2
0-5
*
18.10
17.11
19.45
9.57
24.84
25.39
19.92
16.43
22.85
21.67
19.52
17.71
5-10
*
18.52
16.19
-
8.23
-
-
17.88
-
-
-
-
15.68
10-30
*
16.87
19.32
-
6.4
_
_
_
_
_
*asBiimed same as control
(continued)
-------
TABLE E-7. (continued)
Depth Day8
(cm) 77 84 91 100 105 113 124 133 141 152 159 166
Control
0-5 18.03 16.42 15.45 16.94 16.29 14.43 12.33 13.98 13.09 12.84 19.78 21.73
5-10 14.35 15.81 - 15.17 17.32 13.37 16.08 17.54 13.63 10.70 16.16 15.42
10-30 - - - . -
T-l
0-5 68.72 9.90 11.72 10.94 10.62 12.62 9.25 17.58 - 9.22 - 18.02
5-10 21.51 12 17 13.02 14.37 13.54 11.71 10.93 11.61 21.17 11.28 14.45 11.88
10-30
T-2
0-5 15.05 16 84 16.54 14.27 15.00 15.28 - 12.87 13 11 12.01 13 93 12.33
5-10 15.26 16.09 0.76 23.86 14 40 14.18 38.95 14.16 13.04 14.96 15.55 16.57
10-30
(continued)
-------
TABLE E-7. (continued)
Depth
(cm)
174
181
Days
Control
0-5
15.80
-
5-10
16.25
18.53
10-30
-
-
T-l
0-5
10.75
12.87
5-10
13.38
-
10-30
-
-
T-2
0-5
13.24
10.54
5-10
13.22
13. 72
10-30
-
-
-------
TABLE E-8. ANILINE LEVELS - MIDDLE SOIL LAYERS (5-10 cm)
Aniline
Midd le
Levels
1
2
5
28
34
37
43
50
57
71
ORGANIC
Cont rol
1533
431
3808
2779
66
3567
549
1419
2013
1607
T-l
460
752
779
13
43
8198
22
263
5223
3081
T-2
894
135
2138
6045
89
4320
152
975
2728
1816
Control
5715
1696
8850
13123
4332
9328
8876
4473
3470
2949
T-l
2255
1227
382 2
7612
2395
7058
11438
7896
10555
10825
T-l
565
99
3771
10144
13556
6576
8365
4352
5066
7590
Control
324
1078
4385
2018
3785
2526
2895
2541
1157
4290
T-l
1081
959
1429
524
3156
2128
1339
1229
955
3525
T-2
587
1041
1314
1696
32
4609
1317
3165
2304
1799
(continued )
-------
TABLE E-6 (continued)
Anil ine
Middle
Levels
77
84
100
105
133
141
152
159
166
181
Control
203
57
2176
1
115
49
6520
218
70
23
T-l
327
100
1045
1
484
2829
1
98
45
14
T-2
541
2074
719
823
961
1168
353
81
1510
854
Control
9611
3099
3107
5404
-
3264
2567
68
331
2465
T-l
14143
2263
2637
4507
1434
3261
2162
1887
177
130
T-2
8270
1376
2909
7712
3434
2665
65
1847
232
2605
Control
10450
1406
2098
2284
2263
2958
3352
3111
1778
1285
T-l
3332
1045
3
1
1650
897
1632
558
1465
60
T-2
3499
695
1193
2686
2955
1270
1712
1857
2995
712
-------
APPENDIX F
CHLORDANE DATA
This appendix contains additional supplemental data obtained on land
restoration techniques for the chlordane spill. The following data are included
in this Appendix.
•background soil analyses
•pH of soils as a function of core depth and time
•percent moisture of soils as a function of core
depth and time
343
-------
TABLE F-l. BACKGROUND ANALYSES OF SOILS - CHLORDANE SPILL
Property
Tepth
Organic
Sandy
Clay
Measure
(cm)
Soil
Soil
Soil
pH
0-5
6.9
6.3
5.2
5-10
7.2
7.5
4.5
10-30
7.2
8.1
5.2
% Moisture
0-5
32.5
22.1
16.7
5-10
24.2
23.2
13.5
10-30
20.6
25.2
15.5
Total Phosphorous
0-5
60
13
19
(ppm)
Potassium (ppm)
0-5
55
139
45
Calcium (ppm)
0-5
624
1200
708
Magnesium (ppm)
0-5
57
120
107
344
-------
TABLE F-2. TOP LEVEL SOIL pH VALUES—CHLORDANE
Soil
Type
Soil
Treatment
1
2
Days
6
13
21
27
33
37
49
Organic
Control
7.5
7.4
7.4
7.5
7.5
7.4
7.4
7.5
6.8
T-l
7.7
7.4
7.8
7.6
7.4
8.3
7.9
8.0
7.7
T-2
7.0
7.0
7.1
7.3
7.3
7.4
8.2
9.2
8.6
Sandy
Control
6.6
7.1
6.8
6.8
6.7
7.3
6.7
6.9
7.1
T-l
8.5
9.4
7.5
7.6
7.0
9.0
8.6
8.5
8.3
T-2
6.6
6.7
7.4
7.3
7.5
7.1
8.6
8.7
8.6
Clay
Control
9.6
10.0
10.3
8.5
10.0
9.8
9.7
9.4
9.0
T-l
5.1
6.0
5.8
5.6
5.3
5.1
5.2
5.5
6.3
T-2
6.4
5.4
7.3
8.3
7.4
7.3
9.1
8.9
8.8
345
-------
TABLE F-3. TOP LEVEL PERCENT MOISTURE LEVELS—CHLORDANE
Days
Soil
Type
Soil
Treatment
: 1
2
6
13
21
27
33
37
49
Organic
Control
33.9
31.1
32.7
33.1
32.5
32.1
28.7
28.8
27.4
T-l
35.2
30.4
34.2
30.9
25.2
30.9
31.0
31.9
23.9
T-2
19.4
21.3
11.5
14.5
19.4
24.6
23.3
21.3
14.5
Sandy
Control
25.4
22.9
21.6
23.2
27.1
23.4
22.5
21.6
22.4
T-l
25.0
24.7
30.3
19.8
16.9
26.1
24.2
21.3
15.7
T-2
12.7
25.1
21.9
24.7
23.9
24.5
24.3
26.7
28.2
Clay
Control
16.9
16.7
17.8
13.0
10.4
11.5
13.1
12.0
11.5
T-l
16.6
18.9
16.8
28.9
12.5
13.3
15.4
16.2
15.2
T-2
18.0
15.7
24.6
30.5
15.8
12.5
17.7
15.2
10.8
346
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TABLE F-4. SOIL BACTERIAL POPULATION-CHLORDANE SPILL
Soil
Type
Treatment
Initial
Days
1
6
13
21
Organic
Control
3.6xl07
3.6xl07
2.5xl08
3.3xl08
4.7xl08
T-l
*
6.3xl06
2.7xl09
4.8xl08
2.3xl09
T-2
*
l.OxlO8
3.2xl08
2.7xl08
1.5xl08
Sandy
Control
1.8xl07
3.2xl07
4.8xl08
2.2xl08
3.OxlO8
T-l
*
3.9xl07
1.2xl09
4.5xl08
2.OxlO8
T-2
k
3.1xl06
2.8xl08
—
2.2xl08
Clay
Control
3.9xl06
4.2xl06
9.OxlO6
7.1xl07
1.3xl08
T-l
k
1.7xl07
l.OxlO8
1.4xl08
1.7xl08
T-2
k
1.5xl07
2.9xl08
2.5xl08
4.5xl07
* Assumed same as control.
347
-------
APPENDIX G
2,4-DINITROPHENOL DATA
This Appendix contains additional supplemental data obtained on land
restoration techniques for the 2,4-dinitrophenol spill. The following data are
included in this appendix.
•background soil analyses
•pH of soils as a function of core depth and time
•percent moisture of soils as a function of core
depth and time
348
-------
TABLE G-l.
BACKGROUND
ANALYSES OF
SOILS—DINITROPHENOL
SPILL
Property
Depth
Organic
Sandy
Clay
Measured
(Ccm)
Soil
Soil
Soil
PH
0-5
6.8
5.6
6.7
5-10
6.0
4.6
6.7
10-30
A.6
4.9
6.0
% Organic Matter
0-5
31
23.1
15
5-10
22
20
11
10-30
19
21
13
Total Phosphorus
(0-5)
60
13
19
(ppm)
Potassium (ppm)
(0-5)
55
139
45
Calcium (ppm)
(0-5)
624
1200
708
Magnesium (ppm)
(0-5)
57
120
107
-------
TABLE G-2. TOP LEVEL SOIL pH VALUES—DINITROPHENOL
Days
Soil Type
Treatment
1
2
12
19
23
34
40
Organic
Control
7.3
7.2
6.7
7.0
5.4
7.1
7.2
Treated
6.4
6.0
6.4
9.0
7.8
8.1
8.7
Sandy
Control
5.1
6.2
5.3
5.6
5.3
6.6
5.0
Treated
5.0
6.2
7.2
8.7
8.0
7.3
9.3
Clay
Control
5.8
6.2
4.5
6.1
4.7
7.3
5.8
Treated
5.9
4.7
7.4
9.0
7.7
7.5
8.5
350
-------
TABLE G-3.
TOP LEVEL
PERCENT
MOISTURE
VALUES—
¦DINITROPHENOL
Days
Soil Type
Treatment
1
2
12
19
23
40
Organic
Control
32.7
27.0
28.A
22.9
26.3
19.7
Treated
34.0
34.1
32.7
34.1
30.5
33.7
Sandy
Control
25.0
31.6
24.2
22.6
23.7
13.5
Treated
27.8
26.1
27.2
25.1
18.9
25.2
Clay
Control
28.6
18.1
15.4
11.4
20.7
7.8
Treated
15.5
16.1
19.6
17.3
16.0
8.8
351
-------
TABLE G-4. SOIL BACTERIAL POPULATIONS - DINITROPHENOL SPILL
Days
12
Soil Type
treatment
Organic
Control
Treated
Sand^
Control
Treated
Clay
Control
Treated
init ial
1.6x10®
*
6.7x10®
*
8.9xl07
*
6.OxlO7
3.lxO7
2.7xl06
9.9xl06
5.lxlO7
3.3xl07
6.8xl07
3.6xl06
1 4xl07
1. 7xl07
l.lxlO6
7.9xl07
AO
2. lxlO7
1.8xl07
9.3xl05
3.2x106
1.5xl06
6.3x10^
352
-------
APPENDIX H
CADMIUM NITRATE AND LEAD NITRATE DATA
This Appendix contains additional supplemental data obtained on land
restoration techniques for cadmium nitrate and lead nitrate spills. The
following data are included in this Appendix.
• pH of soil
353
-------
TABLE H-l. SOIL pH LEVELS IN CADMIUM UPTAKE STUDY
Soil Days
Type
Treatment
1
2
3
13
15 '
23
53
68
106
Organic
control
5.5
6.5
6.7
8.2
7.3
7.4
7.2
6.8
6.7
pH(w) lettuce
&
chard
5.5
6.5
7.7
7.2
7.5
7.1
7.1
7.1
7.4
chelated & pH
6.3
6.9
6.6
7.4
7.1
6.9
7.3
7.2
6.8
pH(w) grass
6.1
6.3
6.4
7.2
7.1
7.6
6.6
6.5
7.2
Sandy
control
6.1
6.4
6.4
5.0
4.8
5.6
6.6
6.3
5.5
pH(w) lettuce
&
chard
5.0
5.5
6.4
5.9
6.7
4.5
6.5
7.1
7.0
chelated & pH
4.8
6.7
5.2
5.8
5.0
5.7
6.5
7.1
6.6
pH(w) grass
6.2
6.5
6.2
4.7
5.4
6.3
6.3
7.2
6.4
Clay
cont rol
5.3
4.8
5.0
4.4
5.4
6.5
7.7
7.8
7.6
pH(w) lettuce
&
chard
7.0
6.7
7.1
7.6
7.9
7.2
8.0
7.9
7.0
chelated & pH
6.5
6.6
6.4
6.6
7.3
5.3
7.7
7.5
7.1
pll(w) grass
5.3
6.1
5.8
5.2
5.6
6.9
7.9
7.6
6.8
-------
TABLE H-2. SOIL pH
LEVELS
IN LEAD
UPTAKE
STUDY
Soil
Days
Type
Treatment
1
3
13
15
23
53
68
106
Organlc
Control
5.9
7.5
7.7
7.2
7.5
7.5
6.8
6.8
pH(w) lettuce & chard
6.1
6.7
6.8
6.9
7.5
6.8
6.9
7.2
Chelated & pH
7.1
7.7
6.9
6.9
7.1
7.5
6.3
7.2
pll(w) grass
6.3
6.6
6.9
6.9
7.2
7.0
6.3
6.5
Sandy
Control
5.6
5.2
4.7
4.7
4.8
5.8
6.8
7.4
pH(w) lettuce & chard
5.9
6.4
6.0
6.3
6.4
7.0
7.2
6.0
Chelated & pH
4.4
6.4
5.2
6.2
5.0
5.5
6.2
4.8
pH(w) grass
5.5
6.2
6.0
5.1
4.9
6.4
7.1
5.9
Clay
Control
6.1
5.8
7.7
4.3
4.2
6.7
8.2
5.7
pH(w) lettuce & chard
6.9
5.0
7.8
6.7
7.8
7.7
8.1
7.0
Chelated & pH
6.4
7.1
7.9
4.9
6.6
7.5
7.6
6.8
pll(w) grass
6.9
6.4
7.2
6.2
4.8
6.4
7.2
7.7
------- |