&EPA
United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
EPA/600/2-84/169
June 1985
Research and Development
Liner Materials
Exposed to
Hazardous and Toxic
Wastes
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EPA/600/2-84/169
June 1985
LINER MATERIALS EXPOSED TO
HAZARDOUS AND TOXIC WASTES
by
H. E. Haxo, Jr.
Robert S. Haxo
Nancy A. Nelson
Paul D. Haxo
Richard M. White
Suren Dakessian
Matrecon, Inc.
Oakland, Califorina 94623
Contract No. 68-03-2173
Project Officer
Robert Landreth
Solid and Hazardous Waste Research Division
Hazardous Waste Engineering Research Laboratory
Cincinnati, Ohio 45268
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OH 45268
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DISCLAIMER
The information in this document has been funded wholly or in part
by the United States Environmental Protection Agency under Contract No.
68-03-2173 to Matrecon, Inc. It has been subject to the Agency's peer and
administrative review, and it has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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FOREWORD
The 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 environ-
ment. The complexity of that environment and the interplay of its com-
ponents 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 and 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. '
The following report presents the results of an exploratory experi-
mental research study of the properties and characteristics of a wide range
of potential lining materials to control the migration of polluting species
from on-land waste storage and disposal facilities into the groundwater.
These materials included a compacted native soil, two treated bentonites,
hydraulic asphalt concrete, sprayed-on asphalt, and a wide range of poly-
meric flexible membrane liners that were available during 1975-1980. The
effects on the properties of these materials of exposure to a range of real
wastes and liquid test media have been assessed in a period of up to seven
years.
Francis T. Mayo, Director
Municipal Environmental
Research Laboratory
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ABSTRACT
This exploratory experimental research project was conducted (1975 -
1983) to assess the relative effectiveness and durability of a wide variety
of liner materials when exposed to hazardous wastes under conditions that
simulate different aspects of service in on-land waste storage and disposal
facilities. The materials studied included compacted soil, polymer-treated
bentonite-sand mixtures, soil cement, hydraulic asphalt concrete, sprayed-
on asphalt, and 31 flexible polymeric membranes based on polyvinyl chlor-
ide, chlorinated polyethylene, chlorosulfonated polyethylene, ethylene
propylene rubber, neoprene, butyl rubber, elasticized polyolefin, and
polyester elastomer. Four semi crystalline polymeric sheetings (poly-
butylene, low-density polyethylene, high-density polyethylene, and polypro-
pylene), though not compounded for use as liners, were included in the
study because of their known chemical resistance and use in applications
requiring good chemical and aging resistance.
The lining materials were exposed in test cells to 10 actual waste
liquids, including two acidic wastes, two alkaline wastes, three oily
wastes, a blend of lead wastes, a pesticide waste, and an industrial waste.
The polymeric materials were also exposed to three media of known composi-
tion, deionized water, 5% aqueous solution of salt, and a saturated solu-
tion of low concentration (0.1%) of an organic, tributyl phosphate. The
experimental approach and methodology followed are described. The poly-
meric materials were also exposed to wastes or environmental conditions
under a variety of procedures which included primary one-side exposure,
immersion-type testing, two types of outdoor exposure, and a pouch test.
Some of the exposures were for as long as 2700 days. New methods for the
testing of polymeric materials are presented.
The response of the lining material to the waste liquids and test
media ranged from little or no effect to severe effects and failure.
Oily wastes appeared to have the greatest effect on polymeric membranes.
Some organics, even at low concentrations, can have severe effects in long
exposures as was shown by the lead waste and the dilute but saturated
solution of tributyl phosphate.
Because of the wide differences in the interaction of lining materials
and wastes due to their uncertainty and complexity of composition, compa-
tibility testing of the candidate liner and the specific waste or prototype
of the waste to be impounded should be part of the process for selecting
lining materials for that application.
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This report was submitted in fulfillment of Contract No. 68-03-2173 by
Matrecon, Inc., under the sponsorship of the U.S. Environmental Protection
Agency. This report covers a period from February 1975 to July 1983.
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CONTENTS
Foreword iii
Abstract iv
Figures xii
Tables xv
Abbreviations and Symbols xix
Acknowledgment xxi
1. Introduction and Objectives 1
2. Summary and Conclusions. . 4
Scope of work 4
Lining materials 7
Native soil 7
Asphalt cement 8
Bentonite and sand mixtures 8
Soil-cement 9
Sprayed-on asphalt 9
Polymeric membranes 9
Wastes 10
Test methods 11
Primary exposure tests 13
Immersion test 13
Roof rack exposure 14
Tub test 14
Pouch test 14
Seam strength tests 14
Environmental stress-cracking resistance 15
3. Technical Approach and Research Plan 16
Basic information regarding liners needed by EPA 16
Experimental approach 17
Research plan 19
4. Selection and Characterization of Wastes and Sludges 21
Introduction 21
Selection of specific wastes 22
Description of the wastes in the test program 22
Acidic wastes 22
Alkaline waste 23
Lead waste from gasoline tanks 23
vi
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Oily wastes 23
Pesticide waste 24
Additional wastes and test media 24
Analysis and characterization of the wastes 25
Handling of wastes and filling of exposure cells 27
5. Selection and Properties of Liner Materials 32
Compacted native clay 32
Selection of soil 33
Preparation of compacted soil specimens 36
Admixed liner materials 38
Asphalt concrete (hydraulic) 38
Bentonite-sand admixes 43
Selection 44
Preparation of polymer-modified bentonite-
sand liner specimen 45
Soil-Cement 45
Selection of soil 45
Preparation of compacted soil-cement liners ... 47
Application of surface-sealing coatings 48
Sprayed-on asphalt membrane 49
Polymeric membrane liners 50
Selection of polymeric membranes for exposure testing ... 52
Butyl Rubber (IIR) 53
Chlorinated Polyethylene (CPE) 54
Chlorosulfonated Polyethylene (CSPE) 55
Elasticized Polyolefin (ELPO) 55
Ethylene Propylene Rubber (EPDM) 56
Neoprene (CR) 56
Polybutylene 57
Polyester Elastomer 57
Polyethylene 58
Polypropylene 59
Polyvinyl Chloride (PVC) 59
Testing of polymeric membranes 60
Analytical properties of polymeric membrane liners . . 62
Physical properties of polymeric membrane liners ... 65
Testing of seam strength of factory and
field systems 69
Fabrication and mounting of membrane liner
specimens in cells 71
6. Exposure in Primary Cells 75
Introduction .75
vii
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Design and construction of primary exposure cells and
ancillary equipment 75
Primary exposure cells 75
Rack for holding exposure cells 78
Silica gravel 78
Soils 80
Selection of wastes for exposure to soil liner .... 80
Monitoring the cells 80
Dismantling of cells and testing of soil specimens . . 81
Movement of waste constituents in the soil liners . . 85
Discussion 88
Admixed materials 92
Asphalt concrete 92
Selection of combinations of wastes and liners. . 92
Monitoring of cells 92
Dismantling of cells and recovery and
testing of liners 93
Bentonite-sand mixtures 96
Selection of combinations of wastes and liners. . 96
Monitoring the cells 96
Dismantling of cells 96
Migration of constituents 99
Discussion 99
Soil-cement 99
Selection of combinations of wastes and liners. . 99
Monitoring of cells 100
Effect of Exposure on Properties 100
Analyses and trace metals distribution 101
Discussion 101
Sprayed-on asphalt 101
Preliminary compatibility tests 101
Monitoring of cells 101
Dismantling of cells and recovery and testing
of liners 102
Polymeric membranes 102
Preliminary compatibility testing 104
Monitoring the cells 104
Dismantling of cells and recovery of liners 107
Testing of the exposed polymeric membrane liners . . .108
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Retention of selected properties of liners on
exposure to different wastes 115
Butyl Rubber Membrane 115
Chlorinated Polyethylene (CPE) Membrane 123
Chlorosulfonated Polyethylene (CSPE) Membrane . .124
Elasticized Polyolefin (ELPO) Membrane 126
Ethylene Propylene (EPDM) Membrane 127
Neoprene Membrane 128
Polyester Elastomer (PEL) Membrane 130
Polyvinyl Chloride (PVC) Membrane 131
7. Immersion Testing of Polymeric Membrane Liners 134
Description of method of immersion testing 135
Testing of immersed slabs 135
Measurements on immersed specimens 136
Analytical properties 138
Physical properties 138
Specific combinations of materials and liquids placed
in immersion tests 139
First group of immersion tests 139
Second group of immersion tests .141
Third group of immersion tests 141
Fourth group of immersion tests 142
Fifth group of immersion tests 142
Results of immersion tests 142
Butyl Rubber (IIR) 143
Chlorinated Polyethylene (CPE) 144
Chlorosulfonated Polyethylene (CSPE) 144
Elasticized Polyolefin 14.5
Ethylene Propylene Rubber (EPDM) 146
Neoprene (CR) 146
Polyester Elastomer (PEL) 147
Polyethylene (PE) 147
Polypropylene 149
Polyvinyl Chloride (PVC) 149
Immersion of membranes in saturated aqueous solutions
of tributyl phosphate 150
8. Outdoor Exposure Tests of Polymeric Membrane Liners 153
Introduction 153
IX
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Roof rack exposure 154
Results 154
Tub test 155
Description of the tubs 157
Test procedure 158
Monitoring 158
Results 159
Recovery and testing of first failed elasticized
polyolefin liner exposed in Oil Pond 104. . . .161
Recovery and testing of the second failed
elasticized polyolefin liner exposed
to Oil Pond 104 161
Recovery and testing of the neoprene
liner exposed to Oil Pond 104 ....... .165
Discussion 166
9. Pouch Test for Polymeric Membrane Liner Materials 167
Introduction 167
Basic procedure of the test 168
Fabrication and filling of pouches 168
Monitoring of pouches during exposure 170
Dismantling of pouch after exposure 171
Tests of exposed membranes from pouches 171
Reporting of results 172
Experimental results 173
Combinations of polymeric membranes and
waste liquids 173
Monitoring of pouches during exposure 173
Pouches containing acidic waste, "HN03-HF-HOAc" .173
Monitoring of outer pouches 175
Failure of pouches during exposure 175
Other observations 181
Dissecting of pouches containing the "HN03-HF-HOAc"
acidic waste 181
Condition of the pouch assemblies 181
Weights 182
Analysis of the contents of the pouches
and of the outer bags 182
Physical properties of the pouch walls 182
Comparison between the pouch test and the
immersion test 186
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Permeability 187
Water 187
Permeability of ions 188
Organics 188
Discussion 189
Comparison of permeability results 189
Comparison of retention of physical properties in
pouch and immersion tests 190
Expansion of pouch test method to all polymeric
membranes 190
10. Anlysis of Prolysis Polymeric Membrane Liners 192
References 195
Appendixes
A Summary list of exposures of flexible polymeric membrane
liners to hazardous wastes 199
B Analysis and characterization of waste liquids and
sludges for multiphase samples 200
C EAL Corporation report on the chemical analysis of
five wastes 205
D Major extractable organics recovered from wastes deter-
mined by gas chromatography and mass spectroscopy 219
E Materials for soil and admix liners 220
F Properties of unexposed polymeric membrane liners 221
G Physical properties of unexposed crystalline polymeric
membranes tested at two inches per minute 226
H Materials used in constructing primary exposure cells
and mounting liner specimens 227
I Physical properties of primary liners after waste ex-
posure in cells 228
J-l Exposure of liner specimens in immersion test - Number of
days of immersion 236
J-2 Exposure of liner specimens in immersion test - Dimensional
changes in machine and transverse directions 237
J-3 Exposure of liner specimens in immersion test - Percent
increase in weight 238
J-4 Exposure of liner specimens in immersion test - Percent
volatiles after immersion 239
J-5 Exposure of liner specimens in immersion test - Percent
extractables after immersion 240
xi
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J-6 Exposure of liner specimens in immersion test - Reten-
tion of stress at 100% elongation 241
J-7 Exposure of liner specimens in immersion test - Retention
of elongation at break 242
K Effect on properties of polymeric membrane lining materials
of exposure on roof of laboratory in Oakland, California. . .243
L Volatiles test of unexposed polymeric lining materials. . . .248
M Test for the extractable content of unexposed lining
materials 251
N Procedure for the analysis of unexposed polymeric
membranes by pyrolysis 255
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FIGURES
Number Page
1 Equipment used in the blending of wastes and filling of cells. . . 28
2 Relationship between moisture content at compaction (Pw) and
saturated hydraulic conductivity (K) of Mare Island Soil 35
3 Jig used in compacting the specimens of soil 37
4 Compacted fine-grain soil liner specimen 39
5 Leak-testing of hydraulic asphalt concrete 43
6 Compaction of a soil-cement liner specimen 47
7 Pattern used in coating the soil cement 49
8 Test specimens for long-term exposure of membranes in
primary cells 71
9 Unassembled exposure cell used for membrane liner specimen 72
10 Design of cells for long-term exposure of membrane liners and
soil and admix liners to the different hazardous wastes 76
11 Unassembled exposure cell used for thick admix specimens 77
12 Overall view of the rack holding the exposure cells 79
13 View of cells on the rack 79
14 Monitoring of cells with Mare Island soil liner 84
15 Distribution of cadmium, chromium, copper, lead, mercury, and
nickel in soil liner after exposure to Oil Pond 104 86
16 Distribution of lead in soil liner after exposure to lead waste . . 87
17 Sequence of photographs showing the recovery of the polyvinyl
chloride specimen (No. 59) exposed to the pesticide waste 109
18 Two photographs of the recovered neoprene liner (No. 43)
that had been exposed to the lead waste 110
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Number Page
19 Principal pattern used for dieing out the physical test
specimens from the exposed primary exposure specimens 112
20 Typical pattern for cutting the physical test specimens
from the exposed primary exposure specimens with fabric-
reinforcement 114
21 Special dumbbell for tensile testing of polymeric membrane
specimens after immersion in waste liquids or test media 136
22 Groups of polymeric membrane liners placed in immersion in
different wastes 140
23 Exposure rack loaded with polymeric membrane specimens 154
24 Drawing of the tub used in the roof exposure of polymeric
membrane liners in contact with wastes 157
25 The open exposure tubs lined with polymeric membranes and
partially filled with hazardous wastes 158
26 Drawing of exposed elasticized polyolefin liner 163
27 Thickness of strip of exposed elasticized polyolefin liner .... 163
28 Retention of tensile strength of elasticized polyolefin ex-
posed in the oily waste 164
29 Schematic of pouch assembly 169
30 Pattern for cutting pieces of membranes for making the pouches . . 169
31 Pouch and auxiliary equipment for monitoring the pouches of
polymeric membrane liners 170
32 A pattern used for dieing out test specimens from dismantled
pouch 172
33 Weight changes of the individual pouches P15-P20 177
34 pH of the deionized water in the outer polybutylene bags 177
35 Electrical conductivity of the deionized water in the outer
polyethylene bags 178
xiv
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TABLES
Number Page
1 Waste Liquids Used in Immersion Study of Liners 22
2 Analysis of Hazardous Wastes Used in Project 26
3 Summary of General Physical Properties and Heavy Metals
Contents of Wastes 28
4 Characteristics of Water Used in Preparing Soil
and Admixed Liners 34
5 Water Permeability of Laboratory Compacted Native Clay Soils ... 35
6 Permeability of Compacted Soil Liner Specimens 40
7 Testing of Hydraulic Asphalt Concrete 41
8 Water Permeability of Cores from Hydraulic Asphalt Concrete ... 41
9 Properties and Composition of Hydraulic Asphalt Concrete 42
10 Water Permeability of Modified Bentonite-Sand Specimens 44
11 Water Permeability of Soil-Cement Specimens 46
12 Properties of Emulsified Asphalt Membranes 49
13 Polymers Currently (1983) Used in Membrane Liner Manufacture ... 51
14 Primary Polymeric Membrane Liners Exposed in Cells 53
15 Testing of Polymeric Membrane Liners 62
16 Water Absorption of Primary Polymeric Membrane Liner
Materials at Room Temperature and at 70°C 70
17 Original Strength of Seams in Membrane Liner Specimens
Mounted in Primary Cells 73
18 Wastes Included in Primary Exposure Tests of the Soil Liner ... 81
19 Monitoring of Cells - Collection and Analysis of Seepage
from Cell with Mare Island Soil Liner and Spent Caustic
Waste (W-2) 82
xv
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Number Page
20 Monitoring of Cells - Collection and Analysis of Seepage
from Cell with Mare Island Soil Liner and Waste Pesticide
(W-ll) 83
21 Elemental Analysis Averaged over all Depths for Mare Island Soil. . 85
22 Concentration of Six Chemical Species in Three Wastes 87
23 Contamination of Mare Island Soil With Selected Chemical
Species when Exposed to Oil Pond 104 Waste 88
24 Volume of Oil Pond 104 Required to Percolate through the
0-2 cm Soil Liner 90
25 Amount of Salt Discharged in the Effluent and Average
Permeability Values for Compacted Soil Liners 91
26 Asphalt Concrete (MAC) after Exposure to Hazardous Wastes 94
27 Density and Compressive Strength of Asphalt Concrete (HAC) 97
28 Monitoring of Cells - Collection and Analysis of Seepage From
Cells with Bentonite-A Sand Mixture and Pesticide Waste (W-ll). . . 98
29 Elemental Analysis Averaged over all Depths for Bentonite-B
Sand Liner 99
30 Wastes Used in Exposure Test of Soil-Cement 99
31 Compressive Strength of Soil Cement-Liners after Exposure
to Different Wastes 100
32 Elemental Analysis Averaged over all Depths for Soil Cement .... 101
33 Emulsified Asphalt Sprayed on Nonwoven Fabric after Exposure
to Hazardous Wastes 103
34 Polymeric Membrane Liners Selected for Exposure in Hazardous
Wastes 104
35 Effect of Immersion in Waste on Membrane Liners and
Sealing Materials - Preliminary Screening Study 105
36 Exposure of Polymeric Membrane Liner Specimens in Primary Cells . . 106
37 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Days of Exposure Ill
38 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Percent Volaltiles 116
xvi
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Number Page
39 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Percent Extractables 117
40 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Percent Retention of Elongation at Break 118
41 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Percent Retention of Stress at 100% Elongation 119
42 Seams in Polymeric Membrane Liner Specimens in Primary Cells. . . . 120
43 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Seam Strength in Shear Mode 121
44 Exposure of Polymeric Membrane Liner Specimens in Primary
Cells - Seam Strength in Peel Mode 122
45 Testing of Polymeric Membranes in the Immersion Test 137
46 Analyses of Chlorinated Polyethylene and Polyvinyl Chloride
Membranes Exposed in Saturated TBP Solution 152
47 Outdoor Exposure of Polymeric Membrane Liners on
Roof Rack 156
48 Combinations of Polymeric Liners and Wastes Placed
in Tub Test 159
49 Temperature of Wastes in Tubs on Roof 160
50 Results of Tub Test of First Elasticized Polyolefin Membrane
Exposed to an Oily Waste for 506 Days 162
51 Results of Tub Test of Second Elasticized Polyolefin
Membrane Exposed to an Oily Waste for 1308 Days 164
52 Results of Tub Test of a Neoprene Membrane After
Exposed to an Oily Waste for 1308 Days 165
53 Seam Strength of Neoprene Liner (No. 82) 166
54 Combinations of Polymeric Membranes and Wastes in Pouch Tests . . . 174
55 Pouch Test of Thermoplastic and Partially Crystalline Polymeric
Membranes with Acidic Wastes - Monitoring of Pouches 176
56 Monitoring of Pouch - pH and Electrical Conductivity of Water
in Outer Bag and Weight Changes of Filled Pouches 179
xvi i
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Number Page
57 Pouch Test of Thermoplastic and Partially Crystalline Poly-
meric Membranes with Acidic Waste - Data on Pouch and Waste
Before and After Dismantling 183
58 Pouch Test of Thermoplastic and Partially Crystalline Poly-
meric Membranes with Acidic Waste - Properties of Membranes
After Exposure 184
59 Pouch Test of Thermoplastic and Partially Crystalline Poly-
meric Membranes with Acidic Waste - Retention of Original
Values 185
60 Weight Change of Membranes During Exposure - Comparison of
Pouch and Immersion Tests 186
61 Comparison of Extractables of Exposed Membranes after Pouch
and Immersion Tests with Acidic Waste, "HNOa-HF-HOAc" (W-9) ... 187
62 Comparison of the Retention of Stress at 100% Elongation of
Membranes Exposed to Acidic Waste in Pouch and Immersion Tests. . . 188
63 Relative Order of Permeation of Polymeric Membranes to Water and
Hydrogen Ions, in Pouch Test with Acidic Waste and to Moisture
Vapor in ASTM E96 Test 190
64 Liner Weight Losses Occurring on Pyrolysis and Extraction 193
65 Carbonaceous Residue Following Pyrolysis under N2 at 550°C 193
66 Analyses of Polymeric Liner Membranes by Pyrolysis 194
xvi n
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ABBREVIATIONS
A - (Soil) activity
°C - Celsius
C - Percent of the clay-size fraction
cm - Centimetre
COD - Chemical oxygen demand
CPE - Chlorinated polyethylene
CR - Chloroprene rubber - neoprene
CSPE - Chlorosulfonated polyethylene
CX - Crystalline or partially crystalline thermoplastic
db - On a dried basis
DMK - Dimethyl ketone - acetone
EPDM - Ethylene propylene rubber
ELPO - Elasticized polyolefin
epi - Ends per inch
EPVC - Elasticized polyvinyl chloride
°F - Fahrenheit
FR - Fabric-reinforced polymeric lining material
GC/MS - Gas chromatography/mass spectroscopy
g - Gram
gpm - Gallons per minute
h - Hours
HAC - Hydraulic asphalt cement
HOPE - High-density polyethylene
i.d. - Interior diameter
IIR - Butyl rubber
in. - Inch
ipm - Inches per minute
K - Coefficient of permeability
L - Liter
LDPE - Low-density polyethylene
LLDPE - Linear low-density polyethylene
LTV - Low-temperature vulcanizing (adhesive)
MEK - Methyl ethyl ketone
mL - Millilitres
MP - Megapoise
MPa - Megapascals
MSW - Municipal solid waste
NBR - Nit rile rubber
P - Poise
P - Pouch number
Pw - (Soil) water content
PB - Polybutylene
PE - Polyethylene
PEL - Polyester elastomer
xix
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pen - Penetration
PI - Plasticity index
ppi - Pounds per inch
ppm - Parts per million
psi - Pounds per square inch
PV - Pore volume
PVC - Polyvinyl choride
S-100 - Stress at 100% elongation
S-200 - Stress at 200% elongation
SERL - Sanitary Engineering Research Laboratory
University of California, Berkeley, California
R - Fabric-reinforced
IDS - Total dissolved solids
TGA - Thermogravimetric analysis
THF - Tetrahydrofuran
TP - Thermoplastic (or unvulcanized) polymeric lining material
UV - Ultraviolet light
VCM - Vinyl chloride monomer
W - Waste number
XL - Crosslinked or vulcanized polymeric lining material
pg - Soil bulk density
ymho - Micromho
NOMENCLATURE
AD
AD-AD
AD-LS
BRK
FOR LOCUS OF FAILURE IN ADHESIVE TESTING
Failure within the adhesive
Failure between two coats of adhesive
Failure between adhesive and liner surface
Break of liner materials outside of seam
CL - Failure at clamp jaw site
DEL - Delamination of the liner material
LS - Failure in the bond between the two adhered liner surfaces
METRIC CONVERSION FACTORS
(U.S. CUSTOMARY UNITS TO SI UNITS)
To convert
Multiply by
Inches to centimetres (cm)
Feet to metres
Mils to centimetres (cm)
Mils to millimetres (mm)
Pounds per square inch (psi) to megapascals (MPa)
Pounds per inch (ppi) to kilonewtons per metre (kN/m)
Pounds (force) to Newtons
x 2.54
x 0.3048
x 2.54 x ID"3
x 2.54 x 10-2
x 6.895 x ID-3
x 1.751 x 10-1
x 4.448
U.S. Customary Units are used in this report as they are commercially used
in the United States in the solid wastes industry as well as the liner
production and installation industries.
xx
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ACKNOWLEDGMENTS
The authors wish to acknowledge the guidance of Dr. Clarence Golueke
and Stephen Klein of the Sanitary Engineering Research Laboratory, Univer-
sity of California, Berkeley, California, who were responsible for the
analysis and characterization of the wastes.
We also acknowledge the assistance of Messrs. Reuben Carter and Max
Harrington of Mare Island Naval Shipyard, Vallejo, California, in obtaining
the fine-grain soil, and the cooperation of Industrial Tank Company, for
supplying the hazardous wastes.
We appreciate the assistance of Dr. Harvey Doner of the University of
California, Berkeley, CA, in the analysis and study of the migration of the
trace metals into the soil and admixed materials. We also acknowledge the
assistance of EAL Corporation for their detailed analysis of the wastes
that were used in this project.
The following companies contributed to this project by supplying
samples, information, and technical assistance:
American Colloid Company
Burke Industries, Inc.
Carlisle Syntec Systems
Cooley, Inc.
Dowell, a Division of Dow Chemical Company
E. I. du Pont de Nemours and Company
Exxon Chemical Company
Firestone Tire and Rubber Company
Gaco Western, Inc.
B. F. Goodrich Company
Goodyear Tire and Rubber Company
Industrial Materials Company
Pantasote, Inc.
Phillips Petroleum Company
Plymouth Rubber Company
Polysar Corporation
Quarry Products, Inc.
Ransome Company
Reeves Bros., Inc.
Staff Industries
Union Carbide Company
Watersaver Company
Witco Chemical Corporation
xxi
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We gratefully acknowledge the cooperation of The Asphalt Institute
and The Portland Cement Association.
We also gratefully acknowledge the peer review personnel who reviewed
the draft of this report:
George Alther, International Minerals and Chemical Corporation
Gerald E. Fisher, E. I. du Pont de Nemours and Company
Ronald K. Frobel, U. S. Bureau of Reclamation
Garrie L. Kingburg, Research Triangle Institute
Thomas Leiker, U. S. Bureau of Reclamation
Ronald E. Ney, Jr., U. S. Environmental Protection Agency
Arnold G. Peterson, J. P. Stevens and Company, Inc.
Richard K. Schmidt, Gundle Lining Systems, Inc.
Klaus Stief, Unweltbundesamt, West Germany
Lloyd Timblin, U. S. Bureau of Reclamation
David C. Wilson, AERE Harwell Laboratory, England
William E. Witherow, Carlisle Syntec Systems
Ralph Woodley, Burke Industries, Inc.
xxn
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SECTION 1
INTRODUCTION AND OBJECTIVES
Studies of the land disposal of wastes in the early 1970's clearly
indicated the need for positive control measures to prevent contamination
of the surface water and groundwater systems that might result from on-land
storage and disposal of hazardous wastes. The use of man-made liner
materials of low permeability appeared to be a feasible means of pre-
venting pollutants in hazardous wastes from entering the groundwater. At
the time this project was initiated in February 1975, a variety of lining
materials had been used in various ways for water impoundment and convey-
ance for 20 years or more. Some of these materials had also been used to
line impoundments of brines and some acidic, alkaline, and other waste
waters. At that time, a wide range of materials differing in permeabil-
ity, composition, construction, and cost had been used or were potentially
useful for confining possible pollutants. Available information, however,
as to the performance and service lives of specific materials exposed to
specific wastes was meager. In order to assess the feasibility of using
various materials of low permeability to prevent the migration of pollut-
ants into the groundwater for extended periods of time to guide and, per-
haps, eventually to regulate the use of lining materials in these ap-
plications, the U.S. Environmental Protection Agency (EPA) needed con-
siderably more information.
This project was undertaken in 1975 with the following broad ob-
jectives:
- To determine how a selected group of lining materials is affected
by exposure to a range of typical hazardous wastes over a rela-
tively extended period of time (initially two years).
- To determine the durability and the cost effectiveness of selected
polymeric membranes, sprayed-on membranes, admixed materials, and
natural soils as liners for hazardous waste storage and disposal
facilities.
- To estimate the effective lives of 12 liner materials exposed to
six types of nonradioactive hazardous waste streams under condi-
tions that simulate those encountered in waste impoundment and
disposal facilities.
- To develop information needed for selecting specific lining mate-
rials for containing hazardous wastes in specific installations.
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- To develop methods for assessing the relative merits of the various
lining materials for specific applications and for determining
their service lives.
- To develop indicator tests that could be used in the selection of
lining materials for given applications.
- To assist the EPA in developing effective controls for the proper
disposal and management of hazardous wastes.
The concern in 1975 was whether or not lining materials could success-
fully contain polluting species in hazardous wastes for extended periods.
Thus, this project as originally conceived was primarily an exploratory
experimental investigation to assess, with respect to typical hazardous
wastes, the performance characteristics and durability of lining materials
available at the time the work began. These lining materials were either
commercially available or, as in the case of the admix and soils materials,
prepared from available raw materials. The decision was made in the
original design of the project by the EPA to expose these materials to
actual waste liquids and slurries removed from storage ponds instead of
test solutions or laboratory-manufactured "wastes." It was recognized that
actual wastes are, in most cases, complex mixtures of inorganic and organic
constitutents generated by more than one source, and their exact composi-
tion cannot be determined even though each waste is of a given type.
"Typical" wastes of different types were, therefore, selected, character-
ized, and used in this study.
Since 1975 there have been a number of important developments in liner
technology, particularly with respect to polymeric lining materials. When-
ever appropriate, these developments have been noted in this report. In
addition, some of the newer products were included in some of the secondary
exposures, e.g. the pouch and the immersion studies.
Results of the work on this project have been reported over the past
several years in the Interim Report on the project (Haxo et al, 1977) at
the Second, Fourth, Sixth, Seventh, Eighth, and Ninth EPA Research Symposia
(Haxo, 1976, 1978, 1980a, 1981, 1982, and 1983), papers presented at a
meeting of the American Society for Testing and Materials (Haxo, 1981), at
the Rubber Division, the American Chemical Society, Symposium on the "Role
of Rubber in Water Conservation and Pollution Control" (Haxo, 1980b), and
at the National Conference on Hazardous and Toxic Waste Management held at
the New Jersey Institute of Technology (Haxo, 1980c). In addition, much of
this work has been reported in the Technical Resource Documents, Lining of
Waste Impoundment and Disposal Facilities (Matrecon, 1980 and 1983).
This final report presents the results of the complete project for the
period February, 1975, through July, 1983, and includes information on the
exposure of lining materials for periods of up to 2700 days. Most of the
exposure data, however, are for periods of up to 1350 days. The reported
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long-term tests that were initiated early in this project have been con-
tinued under EPA Contract No. 68-03-2969. Some of the long-term data
obtained in that project are included in this report to present the com-
plete and final results or to present data on which conclusions can be
drawn. In many cases, the adverse effects of exposure to the wastes did
not become apparent until completion of the longer exposure times.
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SECTION 2
SUMMARY AND CONCLUSIONS
SCOPE OF WORK
This exploratory research program was designed to determine the
effects of exposing a broad range of selected liner materials to a variety
of wastes, sludges, and test media under various test conditions for
extended periods of time up to approximately 2700 days. Four broad types
of materials were included in the program:
1. One compacted soil of low permeability.
2. Three admixes, consisting of an asphalt concrete, polymer-treated
bentonite-sand mixtures, and a hydraulic soil-cement.
3. One sprayed-on membrane of an emulsified asphalt on a nonwoven
fabric.
4. Thirty-two different polymeric sheetings based on the following
types of polymers:
- Butyl rubber.
- Chlorinated polyethylene.
- Chlorosulfonated polyethylene.
- Elasticized polyolefin.
- Neoprene.
- Polybutylene.
- Polyester elastomer.
- Polyethylene (low- and high-density).
- Polypropylene.
- Polyvinyl chloride.
Most of the sheetings selected for study in this project were commercial
membranes used for lining pits, ponds, and lagoons. Others were prototype
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materials or sheetings of polymers we felt would be promising as liners.
The polymeric materials selected included a range of sheetings of different
thicknesses and made by different manufacturers, crosslinked and thermo-
plastic variations of some of the same polymers, and a few fabric-rein-
forced sheetings. Some of the commercial materials included samples of
sheetings of polybutylene (PB), low-density polyethylene (LDPE), high-
density polyethylene (HOPE), and polypropylene (PP) which, though they
were not commercial lining materials, were included in the study because of
their promising characteristics and their use in the manufacture of pipes
and containers for handling corrosive chemicals. These latter sheetings
did not contain carbon black nor were they designed specifically for use as
linings for waste disposal facilities. Thin films of LDPE and polybutylene
had been were used previously in the study of liners for MSW landfills
(Haxo et al, 1982).
Note: At the time this project was initiated, lining materials
based on HOPE had not been commercially introduced in the
United States.
The initially-selected actual wastes representing several general
types, included:
- Two acidic wastes, one of which had a pH of less than 1.0.
- Two alkaline wastes, one of which had a pH greater than 12.5.
- One lead waste.
- Three oily wastes.
- One pesticide waste.
These wastes were obtained from ponds in which wastes generated by more
than one source were stored. Later an industrial waste containing high
concentrations of trace metals and some organics was added.
In addition to the real wastes, three test media of known composition
were included for use as reference points:
- Deionized water.
- 5% Solution of salt and water.
- Saturated aqueous solution of tributyl phosphate (0.10%).
The first two media could be used as standard reference points, as many of
the wastes that are encountered contain water and salt. The saturated
solution of tributyl phosphate was included to assess the long-term effect
on polymeric membranes of an organic chemical in a dilute aqueous solution
of known low concentration.
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Four major types of exposure tests of the lining materials were
conducted:
1. One-sided exposure to the wastes. In this exposure test, liner
specimens, about 1 ft^, were mounted in cells and a 1-ft head of
waste was placed on them. The polymeric membrane specimens and the
sprayed-on asphalt specimens included seams. This test was de-
signed to simulate a liner at the bottom of a pond. The perme-
ability of the material could be assessed by collecting seepage
below the liner specimen. Durability was measured by the retention
of properties including seam strength after two exposure periods.
All four types of lining materials were exposed in this type of
exposure test which was the primary exposure test of the study.
These exposures consisted of the "primary" exposures of the project
and the liners studied were the primary liners.
2. Two-sided exposure to the wastes by immersion of liner slabs.
Samples (8 x 8 in.) of 16 polymeric membrane liners were suspended
in the tanks of the above cells containing 13 waste liquids and
test media. In most cases, two specimens of a membrane were placed
in the waste liquid, withdrawn at two different times, and sub-
jected to a series of tests, including measurement of dimensions,
weight increase, volatile content, and extractable content, and
physical tests such as tensile, tear, and puncture.
3. Outdoor exposure. Two types of outdoor exposure were conducted.
The first exposed polymeric membrane samples to weathering, and the
second exposed samples intermittently to both weathering and a
waste. In the first exposure, three slab specimens of each mem-
brane were mounted on a rack placed on the roof of our laboratory
in Oakland, California. One specimen of each membrane was removed
and tested after each of three time periods. The specimens were
measured for dimensional changes and then tested in a manner
similar to those tested in the immersion test. In the second type
of outdoor exposure, sheetings of polymeric membranes were used to
line small tubs which were then loaded with wastes. This test
allowed assessment of the effects of weather and waste exposure on
the liner below, above, and at the interface of the waste and air;
it also assessed the effect of directional orientation with respect
to the sun. The liner specimens in the tubs contained a "field"
seam so that the effect of wastes on seam strength could also be
assessed.
4. A pouch test. This test furnished two types of information regard-
ing a membrane 1iner:
1. Information regarding the permeability of the membrane to
waste constituents.
2. The effect of one-sided exposure of the membrane to a
waste.
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In this test pouches were fabricated from polymeric membranes filled
with wastes and sealed. The sealed pouches were then immersed in deionized
water and exposed for extended periods. The permeability of the membranes
could be assessed by measuring at various time intervals the weight change
of the pouch and the conductivity and pH changes of the deionized water
in which the pouches were placed. When the pouches were eventually
dismantled, dissected, and tested, they also yielded information on one-
sided exposure to wastes.
The duration of these tests ranged up to 2700 days for the primary
tests, 1456 days for the immersion test, 1231 days for the roof rack test,
and more than 2500 days for some of the tubs. Some of the pouch tests ran
as long as 2000 days.
The project was concerned largely with the chemical compatibility of
liner materials as measured by the liner's absorption of the waste solu-
tion, by changes in mechanical properties and, in some cases, by changes in
permeability.
Note: Chemical compatibility of semi crystal 1ine polymeric
materials with various wastes, as measured by environ-
mental stress-cracking, was not addressed in this pro-
ject. These materials were not significant factors in
the USA at the initiation of this project. Studies of
the environmental stress-cracking resistance of semi-
crystalline materials under different conditions are
underway in a current project by Matrecon (EPA Contract
No. 68-03-3169).
In addition to the exposure studies, a variety of analytical tests
were developed for characterizing and fingerprinting the polymeric mem-
branes. These included analyses for ash, volatiles and extractables, and a
pyrolysis test to measure the general composition.
The overall results of the project indicated that the response of the
lining materials to the wastes varied considerably, from apparent compati-
bility to obvious failure. Because liner-waste combinations are highly
specific, compatibility testing is needed as part of the process to select
a liner for a given waste.
Specific conclusions of this work from the viewpoints of lining
materials, wastes, and test methods are presented below.
Lining Materials
Native soil--
Specimens of the native soil (Mare Island) liner showed only modest
effects during the 6.5 years of exposure to five of the waste liquids:
- Low alkalinity waste, "Spent caustic."
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- Lead waste.
- Oily wastes:
"Slurry oil"
"Oil Pond 104."
- Pesticide waste.
Combinations of the soil liner with the acidic wastes had been eliminated
in the screening tests because of apparent incompatibility, as evidenced by
early passage of low pH liquid through a 2-in. core.
The 1-ft thick soil liners showed initial low permeability (2.0-3.1 x
10~8 cm s~l) to all the wastes tested, which they maintained throughout
the exposures. The apparent insensitivity of this soil to various chemi-
cals is probably related to its high ratio of nonclay to clay minerals
in the fraction smaller than 2 urn. Another feature of this soil that may
contribute to its insensitivity was its high salt content; it had been
dredged from the channels in the Carquinez Straits in California at
the mouth of the Sacramento River in San Francisco Bay and had dried on
land. Except for the possible migration of copper, the other five metals
tested (cadmium, chromium, lead, mercury, and nickel) did not appear to
migrate below about the top 2 cm of the liner during 958 days of exposure
to the "Oil Pond 104" waste which contained these trace metals. A liner of
an equivalent initial permeability to water and with high amounts of
smectite may have given different results.
Asphalt Cement--
Combinations of the asphalt concrete and the oily wastes were elimi-
nated in the screening tests. However, in spite of the low permeability
and good mechanical properties of the 2.5-in.-thick asphalt concrete, the
liner was deficient in several other exposures. Both specimens in contact
with the strong acid ("HN03-HF-HOAc") developed leaks; some of the aggre-
gate at the surface was dissolved, and the asphalt itself hardened severely
during exposures that were relatively short (40 and 199 days). Leaks also
developed in the specimens below the "Spent caustic" and lead wastes. The
lead waste contained sufficient oily constituents to cause the asphalt
concrete to become almost a slush. Some seepage also occurred through the
specimens below the liner. We conclude that this type of lining material
should not be used with wastes that contain oily compounds and that the
aggregate proposed for use needs to be thoroughly tested for compatibility
with the waste. Also, a thickness of 2.5 in. may be insufficient even for
water and compatible dilute wastes.
Bentonite and Sand Mixtures--
Polymer-treated bentonite and sand mixtures were eliminated in the
screening test from exposure testing with the acid and strong alkaline
wastes but were tested in cells containing the lead, pesticide, "Slurry
oil," and "Oil Pond 104" wastes. The 5-in. thick specimens exhibited low
8
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permeability (<10~8 cm s'1), though the Bentonite B specimens showed signi-
ficantly lower permeability than did the Bentonite A specimens. This type
of lining material is probably not satisfactory for oily type wastes since
considerable "fingering" of the waste into the liner mass took place during
the 980 days of exposure; however, none of the oil broke through the liner
to be collected in the base. Even though some flow through the liner
occurred, the distribution of the metals at the various depths was uniform.
The use of a soil cover on the liner to produce an overburden could pro-
bably reduce the fingering effect and reduce flow.
Soil-Cement
The 4-in. thick soil-cement specimens showed resistance to "Spent
caustic," the lead waste, the two oily wastes, and the pesticide waste.
Soil-cement had been eliminated from exposure to the strong acid waste
("HN03-HF-HOAc") in the screening test. No seepage occurred in any of
the specimens. In the five recovered and tested, actual increases in
compressive strength occurred. Metal concentrations were uniform through
the depth of the liners.
Note: It must be recognized that these specimens were all small
and not subject to shrinkage or cracking that would be
experienced in large installations.
Sprayed-on Asphalt--
When exposed to the "Spent caustic" waste, the pesticide waste, and
water, the sprayed-on asphalt showed little change in properties. A leak
developed in one of the specimens in a cell containing brine. The sprayed-
on asphalt had been eliminated from exposure testing to the oily wastes
because of their oily contents, and screening tests showed it to be
incompatible with the highly acidic waste ("HN03-HF-HOAc"). In contact
with the lead waste, it softened considerably and in all cases absorbed
water. Compatibility tests would be appropriate when considering sprayed-
on asphalt for lining an impoundment, and all oily or highly acidic wastes
should be avoided.
Polymeric Membranes--
There were major variations in the responses of the polymeric mem-
branes to individual wastes, particularly to those wastes containing oily
constituents. The effects varied from essentially no change during the
exposures to complete failure. Several of the membranes were deleted in
the screening tests from exposure to the oily wastes in the primary cells,
The variations in responses were not only among the different polymer
types, but also within a given polymeric type due to compound variations,
e.g. plasticizer type and amount, crosslinking, and fabric reinforcement.
These results demonstrate the need in the selection and design process for
determining the compatibility of the individual lining material with the
particular waste with which it is to be in contact.
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The general types of membrane liners discussed below include cross-
linked polymers, thermoplastic polymers, semi crystal line polymers, and
fabric-reinforced membranes with coatings based on either crosslinked or
thermoplastic polymers.
Crossl inked polymersThis group of polymeric membranes includes:
- Two based upon butyl rubber.
- Two based on ethylene propylene rubbers.
- Three based on neoprenes.
- One based on chorinated polyethylene.
The membranes include both fabric-reinforced and unreinforced sheetings
which were tested in both the primary and immersion tests.
Crosslinking normally causes a polymer to swell less and be more
resistant to change in liquids. This quality was observed in the lining
materials based on chlorinated polyethylene (CPE) which, in all but one
case, experienced less swelling and fewer changes in properties with the
crosslinked materials. In contrast, a thermoplastic ethylene propylene
rubber (EPDM) sheeting had significantly lower swelling in the wastes than
a crosslinked EPDM, which is the usual type of EPDM sheeting used for
liners. It must be recognized, however, that there are considerable
differences in the EPDM rubbers, some of which can contain some crystal -
linty, which tends to reduce swelling.
The seams of the butyl rubber, EPDM and neoprene were all prepared
with cold-curing adhesives which tended to yield low values. In tests the
failures were in the adhesives.
Thermoplastic po1ymers--The thermoplastic sheetings selected for
this project included:
- Two based on chlorinated polyethylenes.
- Four based on chlorosulfonated polyethylenes.
- Eight based on polyvinyl chlorides.
- One based on an ethylene propylene rubber.
All of these materials tended to be sensitive to the type of waste, in-
dicating the need for compatibility testing before selected for use as a
liner in a waste storage or disposal facility.
Membranes based on polyvinyl chloride (PVC) varied considerably from
sample to sample and in their responses to a given waste liquid. Test
results for the specific materials tested varied from major losses in
10
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weight to significant increases, and from near embrittlenient to severe
softening. This variation indicated the effect of compound differences,
e.g. plasticizers. The need for compatibility testing of the liner with
the waste was quite apparent.
The seams of the membranes based on thermoplastics retained their
strengths during most of the exposures.
Semi crystal line polymersA variety of semi crystal line materials were
exposed in this project, including:
- One elasticized polyolefin.
- One high-density polyethylene.
- Two low-density polyethylenes.
- One polybutylene.
- One polyester elastomer.
- One polypropylene.
Of these semi crystal line polymers, only the elasticized polyolefin (ELPO)
was a commercial product for liner use at the time this project was in-
itiated. The polyester elastomer (PEL) was an experimental material.
The remainder were all commercially-manufactured films, but were not
for liner use. All of the latter were clear and contained no carbon
black. They were tested because their good chemical resistance indicated
potential use in liner materials.
Among the polymeric materials studied in this project, the sheet-
ings of semi crystal line materials showed the least absorption of wastes
and, by and large, retained their physical properties best. Variations
arose in that some of the crystalline materials, particularly the elas-
ticized polyolefin, swelled considerably in wastes that contained oily
constituents. The elasticized polyolefin had the lowest level of crystal-
linity on the polymers in the above group.
The heat-sealed seams in the ELPO and polyester elastomer specimens
essentially maintained their strength during the exposures; for both
specimens, the lower values after exposure reflected softening of the
liner itself.
The polyester elastomer sheeting exposed in the strong acid ("HNO^-
HF-HOAc") failed completely and cracked. The ELPO absorbed considerable
amounts of the alkaline "Slop water" waste and showed a major increase in
permeability after about one year in the pouch test.
Note: Since this project was initiated, new crystalline poly-
meric sheetings based on several of these polymers have
been developed for use as lining materials and have become
commercially available.
11
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Wastes
In terms of their effects on the lining materials, the 13 wastes
and test media used in the project can be grouped as follows:
- Acidic wastes.
- Alkaline wastes.
- Brine and industrial wastes.
- Lead waste.
- Oily wastes.
- Trace organic test liquid.
- Deionized water and pesticide waste.
Overall, the deionized water had the least effect on the membrane
liners except for those based on elastomeric polymers containing chlorine;
in the case of the sheetings based on neoprene, CPE, and CSPE the swell
was greater than in a waste containing salts.
Among the wastes included in the program, those with oily constituents
generally caused the greatest swelling and the greatest loss in the values
of the properties of the polymeric and asphaltic lining materials. These
wastes included the lead waste, the "Slurry oil," "Oil Pond 104," and "Weed
oil."
Two types of nonoily wastes, i.e. acidic and alkaline, caused signi-
ficant loss of plasticizer and stiffening of the PVC specimens.
A trace (<0.1%) of an organic species such as tributyl phosphate in an
aqueous solution caused severe swelling and loss of physical properties of
some membrane liners after long exposure. The effect of immersion in the
dilute, but saturated, tributyl phosphate solution varied considerably
among the 16 membranes, indicating a specificity of liners and organic
constituents. Semi crystal line materials showed the lowest effects of the
trace organics in the wastes.
The nonhomogeneity of wastes and the sampling procedure posed problems,
and could pose major problems, in testing the compatibility of membranes
and wastes in making the selection of a lining material for impounding a
given waste. Some of the wastes stratified so that the waste at the bottom
of a cell or tank had a considerably different composition from that at the
top. Thus the specimens exposed horizontally at the bottom of a cell were
not exposed to the same waste that suspended specimens were exposed to at
the top. Such could also be the case with a pond liner when exposure at
the bottom is compared with exposure near the top. Thus the possibility
exists that a test specimen in a compatibility test may not be exposed to a
representative waste from the impoundment or to a waste from a critical
12
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area in the pond. Two of the wastes were saturated with salts that
crystallized out of the waste onto the liner, thus exposing the liners to
wastes different from the initial waste solutions. Constant agitation of a
nonhomogeneous waste during exposure testing may be a solution, but it
may not result in the worst exposure condition. The effect of agitation
should be studied in order to establish a compatibility test. More
laboratory data are needed to develop background correlations with field
exposure and actual service.
Within their respective groups, the more acidic and the more alkaline
the wastes, the more aggressive to the lining materials. The "Spent
caustic" waste, which is essentially a saturated brine solution, behaved
very much like the 5% brine and the industrial waste.
Test Methods
The various test methods that were used in characterizing the liners
and following changes on exposure to waste liquids revealed significantly
different responses among the liners on exposure to each type of waste.
Generally, some correlations appear to exist among the results obtained by
the different test methods.
Primary Exposure Tests--
The primary exposure cells and the test procedures were satisfactory
for assessing the effects of the waste exposure on the liners. These were
one-sided exposures. The cells acted as permeameters with a head of 1-ft
of waste liquid and yielded permeability data on the soil and bentonite
compositions. The high acidic wastes, however, resulted in corrosion of
the steel containers, presumably through pinholes in the epoxy coating. At
the time the cells were dismantled, those cells that had contained acidic
wastes were so badly damaged that they could not be reconditioned. The
anti-rust paint used on the outside of the cells generally was not satis-
factory for the longer exposure periods; the cells had to be repainted
during service. In more recent projects, at the time the cells were
fabricated, they were epoxy coated on the outside as well as on the inside.
Test duration should be as long as possible. The 12 and 24-month
exposures originally set in the contract were far too short for estimating
service lives unless the latter are relatively short. Also, the number
of exposure periods was inadequate for projecting some of the physical
properties because of inherent errors arising from the nature of these
tests and the problems in handling exposed specimens.
Immersion Test--
The immersion test in which both sides of the membrane were exposed
to waste yielded somewhat faster responses. The test also allowed us to
greatly increase the number of membranes that were exposed.
An immersion test can be adapted for use as a compatibility test
of a lining material with a given waste if at least four time exposures
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are used with at least one month between exposures. However, the immersion
test should be investigated further to develop correlation with actual
experience.
Roof Rack Exposure
The roof rack test as run in this project was an exploratory test to
assess the effect of weather exposure on a selected group of membrane
liners. Conditions of exposure in Oakland, California, are comparatively
mild; however, the exposure period of three and one-third years showed many
of the effects that are encountered in actual exposures of liners in
service. Most of the liner materials are at times exposed to the weather,
although several are generally covered with soil in actual service.
All of the membranes showed some changes in properties but none of
the liners had actually aged to the point at which their properties had
seriously deteriorated. Most of the membranes lost in elongation at break
and in weight and extractable content due to evaporation of plasticizers;
they all shrank and tended to stiffen, but generally gained in tensile
strength. The CSPE membrane gained some weight. The PVC liners showed
surface crazing and were the most severely weathered, as was expected; in
actual service, the PVC liners are generally soil covered.
Tub Test
The tub test demonstrates that different locations within an impound-
ment can have significantly different effects on the retention of pro-
perties by a liner. This test also shows that the most severe effects of
exposure occur at the interface between the waste and the weather.
Pouch Test --
The pouch test used in this project with only thermoplastic and
crystalline membranes shows considerable promise for assessing the effects
of a waste liquid in contact with a polymeric membrane liner. Efforts
should be undertaken to increase the applicability of this type of test to
crosslinked sheeting and to stiff, thick sheetings. The test was run
primarily with thinner sheetings that could be heat-sealed or solvent-
seamed. The pouch tests, however, may have to be run for extended periods
of time to observe long-term effects, and they may require interpretation
until this test procedure has been used extensively.
Seam Strength Tests--
The changes in strength of the seams incorporated in the primary
exposure specimens were tested in both peel and shear modes. The effect of
the exposure on the seam itself is shown best by the peel test; effect of
the change in the shear values generally relate to the effects of the
wastes on the liner itself. We recommend that both tests be performed on
the seams.
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Environment Stress-Cracking Resistance
Note: As high-density polyethylene has become an important
material for the manufacture of liners, accelerated
environmental stress-cracking tests should be developed to
test the compatibility of crystalline polymeric materials
with wastes. The resistance to environmental stress-
cracking among semi crystal line materials is presently
tested by immersions in standard surfactant solutions.
The possible stress-cracking in various waste liquids
needs exploration. These effects are not applicable to
elastomeric and noncrystalline thermoplastic and were not
studied in this project.
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SECTION 3
TECHNICAL APPROACH AND RESEARCH PLAN
BASIC INFORMATION REGARDING LINERS NEEDED BY EPA
AND THE WASTE MANAGEMENT COMMUNITY
The U.S. Environmental Protection Agency, in their report to Congress
(EPA, 1974), concluded that the then existing current management of the
nation's hazardous wastes was "generally inadequate" and that the "public
health and welfare are being unnecessarily threatened by the uncontrolled
discharge of such waste materials into the environment," and recommended
control of the disposal of these wastes. In response, Congress passed the
Resource and Recovery Act of 1976. To implement this law and develop the
necessary controls and regulations, the EPA needed technical data to
establish the types and properties of barrier materials that could be used
to prevent migration of potentially polluting species in a waste storage or
disposal facility from entering and contaminating surface water and ground-
water. From a broader viewpoint, the EPA needed to establish the state of
liner technology and to determine whether the technology existed for
adequate on-land storage and disposal of wastes. They needed to establish
the limitations of the then-current technology and demarcate the problem
areas and the areas of uncertainty toward which future research should be
directed.
At the time this project was initiated (1975), information regarding
the effectiveness, compatibility, and durability of lining materials in
contact with the wide range of hazardous and industrial wastes was very
limited. Man-made materials of low permeability had been used to line
water impoundments and canals for a considerable length of time and much
information regarding these materials had been developed. Requirements
for resistance to the permeation of water in these applications were not
stringent as minor losses of water can be tolerated. Also, the inter-
actions of water with many of these materials were well known. However, in
the case of hazardous wastes, the situation is drastically different. Such
wastes contain a vast array of organic and inorganic constituents, many of
which are toxic; therefore, the tolerance for permeation of waste constitu-
ents from land impoundments is necessarily very low because of potential
contamination and pollution of surface water and groundwater.
A lining material for a waste storage or disposal facility must have
low permeability and maintain its integrity for the time period required.
It should not change in properties; particularly, it should not increase
in permeability. Also, a liner should probably be capable of deforming and
accepting small deformations of the surface on which it is placed.
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Furthermore, information was needed by designers and facility owners
to aid in the selection of materials that could be used in the lining
of disposal facilities. It was desirable while conducting the project to
develop information that would help designers understand the various liner
materials and their properties.
EXPERIMENTAL APPROACH
To meet these broad needs for information our basic approach was
primarily exploratory in nature. As a first step we wanted to extend the
information which we had accumulated in the project relating to liners for
containing municipal solid waste (Haxo et al, 1982). In the two years
after the municipal solid waste project had been initiated in 1973, liner
technology had progressed and several new lining materials had been intro-
duced. We needed to take advantage of these newer materials so that we
could establish the state of current technology. On the other hand, in
order to develop a depth of information on some of the most-used materials,
it was desired to include in this study some of the same membranes that had
been put into exposure with MSW leachate.
The lining materials that were to be investigated were primarily
commercial products. In the case of field-prepared lining materials such
as soils and admixes, standard methods and materials were to be used in
their preparation as test specimens. One or two compacted native soils
were to be included in this set of lining materials. All of the liners in
the exposure studies were to be highly characterized so that information on
them could be transferred to other lining materials of somewhat different
composition and construction.
It was decided from the outset to use real wastes in the exposure
tests. These real wastes were to be typical of the wastes that might be
encountered and might be stored or disposed of on land. The wastes se-
lected and used were also to be highly characterized particularly with
respect to constituents that might be aggressive to lining materials.
Again, such information would aid in developing an understanding of the
effects of wastes on lining materials and could be used in assessing the
aggressiveness of other wastes. The initial program called for six wastes,
but later this number was increased to ten. It was particularly important
to include highly acidic and highly alkaline wastes, and wastes that
contained organic constituents. Consideration of these characteristics
contributed to the selection of the specific wastes that were used.
It was recognized from basic knowledge of materials and past experi-
ence that some combinations of liners and wastes would be incompatible and
could lead to early failures in the test cells. It was desirable to avoid
liner-waste combinations that would probably fail after relatively short
exposures so that maximum use of the equipment and the funds available
could be made. Thus, we selected specific lining materials for exposure to
each waste so that as many combinations as possible could be tested for the
full, predetermined exposure periods. A series of short, preliminary
compatibility tests of candidate lining materials and the wastes were
performed to screen out the obviously incompatible combinations.
17
-------
Exposure conditions should simulate the environment and other aspects
of actual service. To estimate the durability or the service life of a
lining material, the environmental conditions to which it is exposed must
be known and understood. The service conditions encountered by a liner for
a hazardous waste impoundment contrast greatly with those encountered by a
liner in a landfill. In the latter case, the usual environment of a liner
is anaerobic, cool, dark, and continually moist (Haxo, 1976). Also, the
waste fluid or leachate, though variable from landfill to landfill and even
within a landfill, will not be as variable, or as highly concentrated in
pollutants or in constituents that are aggressive to liner materials, as
the waste liquids encountered in a waste disposal facility that contains
industrial, hazardous, and toxic wastes.
Some of the conditions that can be encountered by liners in hazardous
waste impoundments are:
- Exposure to a vast array of different chemical species in direct
contact or under soil cover.
- Exposure to weather, e.g. sunlight, rain, wind, ozone, and heat.
- Wave action of the liquid waste in the pond.
- Intermittent exposure to both waste liquids and weather.
- Low and high temperatures.
- Burrowing and hoofed animals.
- Ground movement.
- Irregularity of the soil above and beneath a liner.
- Changing temperatures during the day.
These conditions must be recognized in evaluating materials in the labora-
tory or on a pilot scale.
The durability of the lining materials was assessed by measuring the
properties after two exposure periods. Each type of material has its own
characteristics which can be used to follow changes with exposure time,
although in all cases low permeability to waste constituents is an es-
sential characteristic that a liner must maintain during exposure to a
waste. Major changes in these characteristics are indicative of lack of
compatibility of a liner material with the waste liquid.
As originally planned, the two exposures were 12 and 24 months; how-
ever, it became apparent by the small changes in properties in the early
stages of the project that longer exposure periods would greatly increase
the value of the test results.
18
-------
RESEARCH PLAN
The basic research plan, with modifications during the course of the
project, consisted of the following:
- To contact the manufacturers of polymeric lining materials and other
organizations involved in liner fabrication and installation regard-
ing the current status of liner technology, and requesting most re-
cent information on their respective products and their performance
characteristics. This aspect of the plan was continued throughout
the entire project as liner technology developed rapidly during this
time with the result that new materials were being offered and
several materials were dropped from the market.
- To design and construct primary cells which simulated the environ-
ment of a liner in service at the bottom of an impoundment. The
liner specimen had to be of sufficient size to allow for the mea-
surement of several physical properties. Initially it was proposed
that the materials under test should line the entire interior of the
primary cells. However, this was not possible with the soil, admix,
and asphaltic lining materials, as it was decided that all materials
should be treated equally. The cells were designed so that the
liner specimens would lie flat underneath a 1-ft head of waste so
that, if waste permeated through a liner specimen, it could be
collected. Specimens of the polymeric membranes were designed to
incorporate a field-type seam.
- To select, collect, and analyze real wastes typical of a variety of
wastes that would commonly be encountered in practice. These in-
cluded acidic, alkaline, lead, oily, and pesticide wastes.
- To obtain, test, and select polymeric membrane lining materials for
the primary exposure test. Bases for selection: if possible, a
range of polymeric types, one thickness, i.e. 30 mil, unreinforced
(no fabric) membrane, and some of the same membranes used in the
study of lining materials for MSW landfills. The remaining mem-
branes were to be tested in immersion and other laboratory exposure
tests.
- To obtain candidate soils, aggregates, and other raw materials for
testing in soil and admix compositions. Once the soils were ob-
tained, to optimize compaction and design for low permeability and
durability to water and wastes and to make the final selection of
materials and design on the basis of these characteristics.
- To prepare the liner specimens, mount them in cells, and load the
cells with the appropriate wastes. Part of the preparation of the
polymeric membrane specimimens included the incorporation of field-
type seams.
- To monitor the test cells and to collect, quantify, and characterize
the seepage.
19
-------
To remove the specimens from the cells at appropriate time intervals
and to measure the properties so as to determine the magnitude of
change during exposure (from the original values for the respective
properties).
To expand the matrix of liner materials and wastes by performing
immersion-type tests in which smaller test specimens would be hung
in the tanks above the primary liners.
To assess the outdoor weathering of selected membranes, both on a
roof rack and as linings of small tubs that contained different
wastes.
To develop methods of characterizing liner materials and of testing
their properties and performance.
To assess the permeability of different polymeric membranes to
different components of wastes by a pouch test in which pouches of
membrane liners could be filled with a waste, sealed, and placed in
deionized water. The weight of the pouch and the electrical con-
ductivity and pH of the deionized water would be monitored to assess
the permeability of water into the pouch and ionic and organic mate-
rial into the water.
20
-------
SECTION 4
SELECTION AND CHARACTERIZATION OF WASTES AND SLUDGES
INTRODUCTION
In designing the original program, EPA desired that real wastes be
used and that as broad a range of types as possible be included. The EPA
project officer identified seven basic types of wastes which should be
included. These were:
1. A strong acidic waste.
2. A strong alkaline waste.
3. A lead waste from gasoline tanks.
4. An oil refinery tank bottom waste.
5. A pesticide sludge.
6. A saturated hydrocarbon sludge.
7. An unsaturated hydrocarbon sludge.
SELECTION OF SPECIFIC WASTES
Twelve individual sludges and wastes were collected by Industrial
Tank, Martinez, California, and a preliminary characterization was made of
one-gallon samples of each in order to select the specific wastes to use.
Eleven of the twelve samples met the basic requirements of composition for
this project. Two hundred gallons of an individual waste were required for
the exposure testing, but several were not collected in that amount. For
example, it was necessary to combine the three lead wastes. Another waste,
that had been labeled "aromatic oil waste," contained little oil and was
volatile; it was discarded. Subsequently, a heavy aromatic oil was ob-
tained from Cities Service.
In several cases the samples that arrived in drums, as well as the
corresponding one-gallon samples, were highly inhomogeneous. Furthermore,
in preliminary analyses, samples from the two sets were found to be con-
siderably different. These differences affected the selection of the
materials, the handling of the waste, and the actual exposure testing of
the liners. Wastes that contained water, oils, and solids stratified.
Generally, the solids fell to the bottom and lay on the liner and the oil
rose to the top and did not directly contact some of the liners, although
some dissolved and emulsified oils did contact the liner. The inhomoge-
neity of the wastes pointed to a basic problem in the testing of liners
with a given waste because it showed that the liner could be in contact
21
-------
with several different materials. Test results also showed the importance
of proper sampling.
The specific wastes that were included in the exposure testing in this
project are listed in Table 1.
TABLE 1. WASTE LIQUIDS USED IN IMMERSION STUDY OF LINERS
Serial
number
2
4
5
7
9
10
11
14
15
16
17
18
19
20
21
Descri
Type
Alkaline
Alkaline
Oily
Oily
Acidic
Acidic
Pesticide
Lead
Oily
Industrial
Brine
Waste description
Identification
"Spent caustic"
"Slop water"
"Oil Pond 104"
"Weed oil"
"HN03-HF-HOAc"
"HFL"
"Weed killer" waste
Lead waste blend
"Slurry oil"
"Basin F" water
"Well 118" water
Deionized water
5% NaCl solution
Trace organic Water saturated with tributyl phosphate (0.1% cone.)
ption of the
50:50 blend of Well 118 water and deionized water
Wastes in the Test Program
Acidic Waste--
Two acid wastes were received from Industrial Tank. The first was
labeled, "HN03-HF-HOAc," and the second, "HFL." Four 55-gallon drums of
the first waste were received. This was a mixed acid containing predom-
inantly (16%) nitric acid, but also included some hydrofluoric acid and
acetic acid. It was predominantly aqueous, was straw colored, and had a
22
-------
trace of suspended solids. The viscosity of this waste was essentially
that of water.
This acidic waste was used in all types of the exposure testing.
Only one drum of the second waste, "HFL," was received. It also was
an aqueous solution. It was used in the latter stages of the project in
immersion tests and in limited exposure testing in the primary cells.
Alkaline Waste--
Two alkaline wastes, labeled "Spent caustic" and "Slop water," were
received from Industrial Tank.
"Spent caustic" wasteFour drums or approximately 200 gallons of
spent caustic was received. It was essentially an aqueous solution, tea
colored, and had crystals in suspension. This waste was saturated and,
when cold, much salt precipitated. The solution had a solids content of
above 20%. It caused considerable problems in the pumping due to the
crystal formation which damaged the centrifugal pumps.
This waste was used in the primary exposure cells, in immersion tests,
and in some of the pouch tests.
"Slop water" wasteOnly one drum of this waste was received. It
also was an aqueous solution with a high salt concentration and a somewhat
higher pH than the spent caustic. It was used in immersion and pouch tests
and in a limited number of cells.
Lead Waste From Gasoline Storage Tanks--
Three different lead wastes (identified as W-3, W-8, and W-12) were
initially received from Industrial Tank. In order to have sufficient lead
waste for the primary exposure test, the three were combined to yield four
drums of waste and assigned the Matrecon serial number W-14. This combined
waste had a strong gasoline odor; it contained some low boiling fractions,
lead compounds, and other additives. However, it was basically an aqueous
waste. These wastes were obtained in the washing of tanks containing
leaded gasolines.
This waste was used in the primary exposure cells, in immersion tests,
and in some of the pouch tests.
Oily Wastes--
Several oily wastes of substantially different character were obtained
and included both unsaturated and saturated oils. These included wastes
labeled "Oil Pond 104," "Slurry oil," and "Weed oil."
"Oil Pond 104" wasteFive drums of waste from "Oil Pond 104" were
received and appeared to contain dispersed water. However, all of the
tests run on this waste showed it contained oily material and solids. The
23
-------
oil phase contained both saturated and unsaturated oils. It was a rela-
tively viscous oil used as a road oil which required some heating in order
to be handled and poured.
The "Oil Pond 104" waste was used in the primary exposure tests and in
the immersion tests.
"Slurry oil" wasteOne hundred gallons of "Slurry oil" waste was
received from Cities Service in Louisiana. It was a heavy highly condensed
hydrocarbon and contained several percent of suspended solids believed to
be residual catalysts. For this test, it was considered to be an "Aromatic
oil" waste. It was necessary to heat this oil in order to pump it into the
cells. Because of the lesser quantity of oil, its use in the primary cells
was limited.
Four drums of another oily waste were received from Industrial Tank
which were labeled "Aromatic oil" waste. However, the oil content of this
waste was small and highly volatile. Consequently, it was not used in any
of the tests because, in the loosely covered cells that were used, the oily
component would have evaporated and there was insufficient waste to replen-
ish the cells.
"Weed oil" wasteOne drum of "Weed oil" waste was received from
Industrial Tank.TfTwas predominantly an aqueous waste that contained low
molecular weight hydrocarbons which appeared, by subsequent tests, to have
been highly aromatic. The oil fraction had been used as a "Weed killer"
for spraying between the ties on railroad tracks.
The "Weed oil" waste was used in immersion tests, in pouch tests, and
in a limited number of cells.
Pesticide Waste
Five drums of a waste labeled "Weed killer" were received from Indus-
trial Tank. This waste was primarily a wash water which contained some
suspended clays and a herbicide. The solids settled out rather rapidly
after stirring.
This waste was used in the primary cells and in the immersion tests.
Additional Wastes and Test Media--
In addition to the wastes discussed above, which were used in the
major exposure of this project, several additional wastes and test media
were added to the project, primarily for use in immersion tests. Some
exposure cells were filled with these wastes as a part of the immersion
tests. Consequently, some of the liners were exposed to them as primary
liners. These wastes included:
- An industrial waste, labeled "Basin F," which contained both metal
and organic constituents.
24
-------
- A contaminated water, labeled "Well 118."
- Deionized water.
- A brine consisting of a 5% aqueous solution of NaCl.
- A saturated solution of tributyl phosphate in distilled water.
The last three media are controlled reference compositions. Deionized
water was included to assess the exposure by the different liner materials
in a medium of zero concentration of the different dissolved constituents
which would allow estimation of the effects of concentrations. The 5% NaCl
brine has a moderate salt content in the range of municipal solid waste
leachate; it is a reference material used in the immersion testing of
polymeric materials and has moderate concentrations of ions. Also, we used
it in pouch testing of membranes so that the ions could be traced. The
last immersion medium was incorporated into the test program to assess the
effects of trace amounts of organics in solution; tributyl phosphate which
has a slight solubility in water (0.1% at 23°C) was used for this purposes.
ANALYSIS AND CHARACTERIZATION OF THE WASTES
Inasmuch as the wastes being used were real wastes, which were not
only multiphase but also highly complex from the standpoint of composition,
it was necessary to perform relatively intensive analyses in order that the
components in the wastes that were aggressive toward different liners could
be identified. It was particularly important to know as much as possible
about the quality of the waste in contact with the liner under test.
During the course of the project, these wastes were subjected to several
analyses to develop this information. Initial analyses were performed by
the Sanitary Engineering Research Laboratory (SERL) of the University of
California, Berkeley. At that time no consistent set of procedures had
been established to analyze these wastes. The initial analyses did not
recognize the multiphase character of the wastes as they were treated as
single materials. Following the description of the analyses used by Dr.
Robert Stephens (1976) of California Health Services, our analytical
procedure was modified to follow a procedure in which the waste was
separated by either centrifugation or other appropriate method into:
- An organic liquid phase containing dissolved organics and dissolved
water.
- An aqueous phase containing dissolved organics and dissolved inor-
ganics.
- A solids phase which can be inorganic or organic solids.
Details of the analytical procedure are described in Appendix B and results
of the analyses are presented in Table 2. The analyses are based upon
samples of the blends of the wastes as they were loaded into the cells.
The procedure for the blending from the several drums is described in the
next section.
25
-------
TABLE 2. ANALYSIS OF HAZARDOUS WASTES USED IN PROJECT
Phases and tests
Separation of phases
Phase I , aqueous
insoluble organic
1 iquid, weight %
Phase 1 1 , aqueous
phase, weight %
Phase III , sol id
phase, weight %
Phase I - Organic
Wei ght %
Flash point0, °C
Viscosityd, cP
At 20°C
At 30°C
«ater content , *
Organic group8
-sonal tenes , %
Po'ar compounds, *
Saturated hydro-
carbons , *
Aromatics, "
^ead, nq/L
Phase II - Aqueous
pH
Weight %
Sol ids in solution, %
Total
Volatile
Solids, total g/L
Volatiles, g/L
Total dissolved, g/L
Volatiles dissolved, g/L
Total suspended, g/L
Volatiles suspended, g/L
Alkal imty, g CaC03/L
Oil and grease g/L
Soluble volatile
orgam cs , rl/ L
Lead, mq/L
Phase III - Solids
Weight %
Flammabi 1 i ty
Flame
Color
SmoKe
Sol ics, %
C'-ganic,
Inorganic, ',
Water extract , mg/g
pn
Ac i d i c
"HNOi-hF-
"HFL" HOAc"b
(W-10) (W-9)
0 0
100 100
0 0
0
... ...
... ...
...
4.8 1.5
100
2.48 0.77
0.9 0.12
140
15
137
7.0
15.0
9.0
...
0.0
Q.G
za*
0
... ...
... ...
Al kal me
"Slop- "Spent
water" caustic"b
(W-4-) (W-2)
0 0
100 95.1
0 4.9
0
... ...
...
... ...
... ...
12.0 11.3
95.1
22.43 22.07
5.09 1.61
234.5
24.2
234.5
24.0
0.04
0.01
8.69
0.02
0.15
5.0f
4.9
Yes
Orange
No
8.9
91.1
122.4
5.2
Wastes8
"Lead "Slurry
Waste"b oil"
(W-14) (W-15)
5.0 98
86.2 0
3.4 2.0
10.4 98
<20 174
3200
660
0
3.1
4.0
... 3.1
59.7
530 '...
7.6
86.2 0
0.9
0.35
3.23
1.62
2.66
1.14
0.41
0.28
1.06/28
0.15 ...
1.0
13
3.4 2.0
. .
22.5
77 ^
43.8
7.4
Oily waste
"Oil Pond "Weed
104"b oil"
(W-5) fW-7)
89 20.6
0 78.4
11 0
89 20.6
157
300
124
17
9.6
12.5
37.9
339
170f
7.5
0 78.4
36 1.81
31 1.0
... ' 9.10
3.45
1.75
11.0
Yes
73.9
21.1
11.2
8.4 ...
Pesti-
cide
"Weed
killer"b
fW-11)
0
99.5
0.5
0
...
. .
3.1
99.5
0.78
0.46
6.78
3.32
6.62
3.22
0.16
0.10
25
0.05
0.8
1.4f
0.5
Yes
Crange
'.0
5C .4
-9.5
3.5
2.5
a^atrecon waste serial number shown below icentlfication.
^Analyzed after exposure.
CASTM 092.
°ASTM 02983.
eASTM 02007-69, in percent By weignt.
r~Total lead content of the waste.
26
-------
These results, however, did not identify specific constituents mate-
rials in the wastes. Consequently, five of the real wastes were subjected
to a more intensive analysis which included gas chromatography/mass spec-
troscopy (6C/MS). These analyses were performed by EAL Corporation of
Richmond, California (Appendix C). The wastes analyzed were:
- Acidic waste ("HN03-HF-HOAc"), W-9.
- Alkaline waste ("Spent caustic"), W-2.
- Lead waste blend, W-14.
- "Oil Pond 104" waste, W-5.
- Pesticide waste ("Weed killer"), W-ll.
In these analyses, the heavy metals were analyzed as well as the organic
constituents. A summary of these results is presented in Table 3. The
full report from EAL Corporation, except for the GC scans, is presented in
Appendix C.
The samples used in these analyses were taken from respective blends
of wastes that were recovered from the cells that contained the membrane
liner specimens at the time the cells were dismantled. The blends of the
wastes from these cell were used because it was felt that they reflected
the composition of the original wastes, though scavenging of some com-
ponents might have taken place and some volatiles may have been lost.
It was recognized that the organics would be absorbed by the polymeric
liner materials and that the degree of absorption would depend on the
organic constituent and its concentration. The GC/MS data from EAL Corpo-
ration was reviewed for three of the wastes that contained organics, i.e.
the lead waste, the pesticide waste, and the "Oil Pond 104" waste. The
concentrations of some of the constituents that appeared on the GC/MS scan
are presented in Table 3. Only two compounds, butyl benzene phthalate and
dibutyl phthalate, were found in all three wastes. The oily hydrocarbon
constituents, however, were not included which, in the case of the lead
waste and the "Oil Pond 104" waste, are the major organic constituents. It
would have been desirable to analyze the extractables in the exposed
liners for these constituents but that was beyond the scope of the project.
HANDLING OF WASTES AND FILLING OF EXPOSURE CELLS
When the exposure cells were loaded with wastes, only five of the six
types of wastes were available in sufficient quantities, i.e. 200 gal or
four drums, to fill the desired number of cells:
- Acidic waste ("HN03-HF-HOAc"), W-9.
- Alkaline waste ("Spent caustic"), W-2.
27
-------
TABLE 3. SUMMARY OF GENERAL PHYSICAL PROPERTIES AND HEAVY MtTALS CONTENT OF WASTES3
ro
CO
Phases and tests
Phase I, aqueous insoluble organic liquid, weight %
Phase II, aqueous, weight %
Phase III, solids, weight %
pH, aqueous phase
Specific gravity, aqueous phase
organic phase
Flash point, °C
Metals analysis'', ing/L:
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thai 1 lum
Zinc
Barium
Cobalt
Molybdenum
Vanadium
Titanium
Organolead
Boron
Acidic
"MN03-HF-HOAc"
(W-9 Rec)
2.6
96.3
1.1
0.5
1.07
c
None, boils
9.6
0.19
<0.2
0.22
22
5.6
28
<0.003
9.0
<1
<0.05
0.21
42
5.0
2.9
0.8
<2.5
19
c
c
Alkaline
"Spent caustic"
(W-2 Rec)
3.4
73.1
23.5
7.7
1.19
c
None, boils
50
<0.02
<0.2
0.6
<0.8
2.3
5.0
<0.003
1.8
<1
0.33
0.03
8.2
19
24
2.0
5.1
12
c
c
"Lead waste
blendb"
(W-14 Rec)
13.6
86.2
0.2
7.6
0.97
0.79
<0°C
87
<0.02
<0.2
<0.76
1.9
1.1
95
0.06
0.9
<1
<0.07
<0.02
64
4.0
7.8
0.44
<2.7
8.5
32
8.1
Oi ly waste
"Oil Pond 104"
(W-5 Rec)
99.0
0.6
0.4
c
c
0.92
None, bolls
500
<0.02
<0.4
8.0
290
33
170
1.6
4.0
<1
12
<0.02
450
<5
40
0.1
10
230
c
c
Pesticide
"Weed Killer"
(W-ll Rec)
0.24
99.4
0.4
2.6
1.00
c
None, boils
9.0
<0.02
<0.2
<0.15
5.4
9.2
1.4
< 0.003
24.5
<1
<0.05
<0.02
150
4.8
1.2
0.5
<2.5
3.0
c
26
aAnalyses performed by EAL Corporation, Richmond, CA, on blends of wastes recovered from exposure cells with polymeric membrane
liners. See Appendix C for full report of FAL Corporation, except for GC/MS scans.
bData combined for aqueous and organic phases.
cNot applicable or no data.
^Atomic absorption analysis.
-------
- Lead waste blend, W-14.
- "Oil Pond 104" waste, W-5.
- Pesticide waste ("Weed killer"), W-ll.
All of the wastes were received in closed-head, 55-gal drums and were much
lower in viscosity than had been anticipated. It was originally expected
that they would be sludge-like and could be handled with buckets from
open-top drums. Furthermore, some were found to be
consisting of two liquid phases and particulate solids.
very inhomogeneous,
Since the waste of
a given type should have the same composition in all the cells in which it
was placed, the waste from the different drums had to be thoroughly mixed
and blended before it was added to the cells. Pumping the wastes from drum
to drum and into the individual exposure cells appeared to be the best way
to handle waste and reduce the chances for spillage. The equipment which
was set up to mix and pump these wastes in shown in Figure 1.
Figure 1. Equipment used in the blending of wastes and filling of cells.
It was necessary to obtain a pump which was compatible with the
wastes, self-priming, able to pump solids in suspension, and had sufficient
capacity to transfer the contents of a 55-gal drum in 10 minutes. A
flexible impeller pump was obtained which had an epoxy pump body and a
totally enclosed motor which allowed hosing down of the pump without
getting water into the motor. The rated capacity was 7 gal per-minute.
Both the impeller and the pump body were replaceable in the event either
29
-------
was damaged by the wastes. The plan for the mixing and blending of each
waste was:
1. To mix thoroughly the contents of each drum by pumping them into
an open-top drum equipped with a 1750 rpm mixer, with dual pro-
pellers and a polyethylene liner, and mixing with the remaining
solids flushed from the original 55-gallon drum.
2. To transfer one-fourth of the contents to each of four additional
open-top drums for blending.
3. To accumulate the mixed quantities in the open-top blending drums
and mix each drum thoroughly.
4. To pump the wastes from the open-top blending drums into the
individual cells.
Thus, each exposure cell received an aliquot of the waste of the same
composition as that received by every other cell containing that waste.
Five-gallon samples of the individual wastes were withdrawn for the
analysis described above.
The wastes were loaded in the cells in the order of anticipated
increasing difficulty, based on viscosity and the apparent amount of
solids. The "Pesticide" having the consistency of water was processed
first, without problems, using the flexible impeller pump.
The "Spent caustic" waste appeared to be the next easiest to handle,
as it was less corrosive than the strong acid ("HNC^-HF-HOAc") waste and
appeared to be an aqueous solution. However, before two drums of the
caustic had been mixed and transferred, undissolved salts wore away the
epoxy body and faceplate of the pump and it ceased to operate. To solve
this problem, a second pump, a centrifugal type of 20 gal per minute, was
obtained. The impeller and housing are made of cast iron which was more
resistant to the abrasion of the salts in the caustic waste than was the
epoxy body of the first pump. Furthermore, the centrifugal pumping action
did not depend upon close fitting parts and handled particles up to 3/8 in.
in diameter.
A strainer was placed over the end of the inlet pipe to strain large
particles when transferring from the closed-head drums. These large
particles were eventually broken-up manually to a pumpable size, and
flushed out of the drum. The shearing action of the mixer in the open-head
drum further disintegrated these insoluble salts.
To fill the 5-gal individual exposure cells using the 20 gpm centri-
fugal pump, it was necessary to reduce the flow by putting a "T" in the
system and circulating a portion of the waste. This pumping system worked
very well with the caustic waste.
30
-------
There was an insufficient amount of a single lead waste to fill the
primary exposure cells; consequently, the three different lead wastes which
were available were combined by the mixing and blending process described
above to yield the four drums needed to fill the exposure cells. The
centrifugal pump was used in the mixing, blending, and transferring of the
Lead wastes.
The saturated and unsaturated oil waste was viscous and had to be
pumped with the flexible impeller pump. Pumping and blending this oily
waste was speeded slightly by warming it with a mantle drum heater.
As the flexible impeller pump is resistant to acids, it was used to
pump the "HN03-HF-HOAc" waste. The acid would have attacked the cast
iron of the centrifugal pump, changing both the character of the waste and
of the pump.
The sixth primary waste, the slurry oil, was highly viscous and only
two drums were available. The blending of the two was dropped and the
cells were loaded directly after heating with electric blankets and homo-
genizing the contents of each drum separately.
All the remaining wastes or media were homogeneous and low in vis-
cosity and posed no problem in handling.
31
-------
SECTION 5
SELECTION AND PROPERTIES OF LINER MATERIALS
To meet the basic objective of this study of the effect on liner
materials of contact with different hazardous wastes, a broad spectrum of
potentially satisfactory materials was considered. These materials in-
cluded compacted native clay soils, admixed materials, such as soil
cements, asphaltic concrete and bentonite, sprayed-on membranes, and
polymeric membranes, all of which had found wide use for lining canals,
reservoirs, ponds, and other water-retention and conveyance facilities.
Though the performance of all these materials with respect to water was
well known, their performance and durability with respect to waste liquids
containing dissolved inorganics, organics, and oils were uncertain.
The materials selected as liners for the primary exposure test were:
- One fine-grain native soil.
- Three admixed materials:
Asphalt concrete (hydraulic)
Bentonite/sand mixture
Soil-cement.
- One sprayed-on asphalt membrane.
- Eight commercial or developmental polymeric membranes.
The specific materials and the test methods used in characterizing each
material are described in the following subsections. Also described is the
preparation of the test specimens mounted in the cells.
COMPACTED NATIVE CLAY
A soil liner is made from soil material that is either on or near the
waste disposal site. The soil is treated, remolded, and/or compacted so as
to form a layer of low permeability. Because of their general availability
and economic considerations, soils generally have been, and remain, the
first material considered for lining a waste containment facility. The
initial study of a site will usually include an assessment, based on
engineering, environmental, and economic criteria, of the characteristics
of the available native soil to determine whether or not it can be used to
produce an effective liner for the particular waste to be contained.
32
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Low permeability is the most important requirement of a soil to be
used as a liner for a waste impoundment. However, in addition to low
permeability, the soil liner also should adsorb the potentially polluting
species, at least temporarily. Both low permeability and high adsorption
capacity of a soil are often associated with the presence of soil fines.
Thus, the proportion of clay size particles (less than 2 \im) is an im-
portant consideration when assessing a soil as a potential lining material.
A specific limiting value of clay-size particles cannot be stated categor-
ically because both soil permeability and adsorption capacity are dependent
on other factors not directly related to the proportion of fines. These
other factors include the gradation and the degree of weathering of the
nonclay fraction and the physicochemical and mineralogical properties of
the clay fraction. Depending on these properties and on the required
permeability to water, which in general will be in the 10~9 to 10~6 cm s~l
range, the acceptable proportion of fines in a soil liner will most likely
be greater than 15-20% of the soil mass.
Selection of Soil
Since only one soil was to be tested in this project, we felt that it
should have as low a permeability as possible and should have minimal
physicochemical interaction with the wastes. Several fine-grain soils were
obtained and tested; they included:
1. A soil material used for "mudjacking" of portland cement concrete
pavement.
2. A clay used for constructing tennis courts and baseball diamonds.
3. A soil used to line a waste pond at a power plant in Moapa,
Nevada.
4. A soil material of fines which was a by-product of washing crushed
graywacke sandstone and which had been used to construct a cover
of low permeability over a chemical waste dump.
5. A very fine silt that had been dredged from the Carquinez Strait
and the lower Napa River.
The last soil was reported to us as having low permeability and was ob-
tained at the Mare Island Naval Shipyard, Vallejo, California.
These fine-grain soils were evaluated at different water contents in
the laboratory by measuring the hydraulic conductivity of remolded speci-
mens with a triaxial, back pressure permeameter (Vallerga and Hicks, 1968)
to determine the minimum permeability that could be obtained with each
soil. Soil samples were oven-dried and then allowed to come to equilibrium
at room temperature, which took approximately 3 weeks. Test specimens were
made by mixing 200 g of dried soil with predetermined amounts of tap water
(Table 4) and compacted in a 2-in. diameter, 2-in. deep mold, using an
impact-action hand drill with a 0.5-in. diameter foot, followed by 2
33
-------
TABLE 4. CHARACTERISTICS OF WATER USED IN PREPARING
SOIL AND ADMIXED LINERS
Concentration, mg/L
Constituent or property except pH and conductivity
Cations
Calcium, Ca 6.0
Magnesium, Mg 0.6
Sodium, Na 1.3
Potassium, K 0.5
Anions
Chloride, Cl 2.0
Carbonate, C03 1.1
Sulfate, S04 0.9
Nitrate, N03 0.05
Bicarbonate, HC03 18.0
Phosphate, P04 0.013
Other
Hardness, total as CaC03 17.5
Alkalinity, as CaC03 17
Total dissolved solids 33
pH 9.1
Electrical conductivity, ymhos/cm 45
Source: East Bay Municipal Utility District, Oakland, California,
December 1975.
minutes double-end static compaction at 7,000 Ib. The permeabilities were
determined with a back pressure of 1.0 atm, a confining pressure of 1.2-1.4
atm, and a gradient of around 25. The amount of time specimens were
pressurized before a run varied. The results are shown in Table 5.
The fine silt dredged from Carquinez Strait, subsequently called Mare
Island soil, was selected for exposure testing in this project. The
permeability of undisturbed cores cut from the water-laid deposits was
between 10~8 and 10~7 cm s~l with a similar range found on laboratory-
compacted specimens prepared at water contents ranging from 14% to 30%
(Table 5).
Figure 2 shows that a small variation in permeability takes place over
a considerable range of moisture contents. This was the first clue to the
fact that, although clayey in terms of the size of the dominant particle
fraction, the Mare Island soil is actually of very low concentration in
active clay minerals. The minimal permeability was obtained around a
moisture content of 22% which, assuming a 95% saturation and a specific
density of 2.65 g cm~3, indicates a soil bulk density of 1.64 g cm~3.
Sieve analysis of the soil (ASTM D1140-54) showed more than 98% pas-
sed the 200 mesh sieve (75 ym) and almost 95% passed the 325 mesh sieve
34
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TABLE 5. WATER PERMEABILITY OF LABORATORY COMPACTED NATIVE CLAY SOILS
Soila
Water*3, parts
per 100 dry
soil
Coefficient of permeabi1ityc
cm s
-1
in. yr
i
Tennis court clay
Mudjacking soil
Mudjacking soil
Moapa, Nevada, #2
Moapa, Nevada, #2
Graywacke fines
Graywacke fines
Fine silt dredged from
Carquinez Strait -
"Mare Island Soil"
10
10
11
15
17
12
15
30
28
25
20
18
16
14
4
1
7
1
4
4
2
8
7
9
6
7
1
1
.0
.8
.9
.7
.1
.9
.8
.2
.8
.0
.5
.3
.1
.2
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ID"5
ID'5
10-6
10-7
10-8
10~6
10-7
10-8
10-8
ID'8
10-8
10-8
10-7
10-7
497
223
2.
0.
61
3
1.
0.
1.
0.
0.
1.
1.
98
10
51
.0
.5
02
97
12
81
91
37
49
aCarbonate content of soils: Graywacke fines soil contains some carbo-
nate; Moapa soil contains more carbonate; Carquinez Strait silt con-
tains no carbonate.
^Soils mixed with various amounts of water, compacted, and tested to
determine water content to achieve minimum permeability.
cMeasured with triaxial, back pressure permeameter (Vallerga and Hicks,
1968).
O
WATER CONTENT (P ), PARTS PER 100 DRY SOIL
Figure 2. Relationship between moisture content (Pw) at compaction and
saturated hydraulic conductivity (K) of Mare Island soil.
35
-------
(45 pm). These results were consistent with particle-size data determined
by hydrometer analysis (ASTM D422-63) which indicated that more than 50% of
the soil mass was made up of clay-size particles (2 urn).
The consistency of the Mare Island soil was also determined. The
liquid limit, using the standard procedure with Casagrande's apparatus
(ASTM D42366), was found to have an average value of 65%. The lower
plastic limit which averaged 47% was much more difficult to obtain because
of the number of tests required for establishing an accurate value. The
plasticity index (the difference between the plastic limit and the liquid
limit) of the soil is 18%; thus, qualitatively the soil is slightly
plastic. The activity of the clay fraction (the plasticity index divided
by the percent of soil mass made up of clay-size particles) was very low,
i.e. 0.36, which almost excludes the presence of any smectite type of
minerals. This finding deserves a special discussion: when soils are
chosen for waste-disposal sites, it is often considered an advantage to
have a soil with a large proportion of smectite clay. Such a soil is
considered good because the characteristic particle size of a smectitic
clay is the smallest among clay mineral categories and thus the consensus
is that a smectite clay should result in the liner of lowest permeability;
the high cation exchange capacity of this clay should also help in tem-
porarily retaining cationic species. While this may be the case, it is
also true that an inert, nonsmectitic clay has the advantage of being
resistant to physicochemical alterations which may lead to hydromechanical
changes. In the case of the Mare Island soil, its low activity indicated
the presence of nonactive clay; thus, the likelihood that the range of
permeability found when water was the percolating solution would be main-
tained upon subsequent use of hazardous wastes. In the next subsection, we
present experimental results that will prove this was the case.
The Mare Island soil had a high concentration of soluble salts (5.5 g/
100 g dry soil) and a pH of 6.5.
Preparation of Compacted Soil Specimens
The soil for the exposure test specimens was compacted into 13-in.-
high spacers, which were coated on the inside with primer, Epoxy 2, and
sandblasting sand. The compacted soil measured 12 x 17 x 12 inches.
An attempt was made initially to compact the soil in a spacer which
had been bolted onto the base, but the assembly was too flexible; the
bottom of the base and the sides of the spacer flexed with each impact of a
tamper. The bond between the soil and the spacer was not tight and it was
felt that the lowest potential water permeability was not achieved. It
was, therefore, decided to compact the soil in the spacer first and mount
the specimens onto the base. A wooden frame was constructed (Figure 3) in
which the spacer was held tightly to prevent bulging of the sides and the
whole assembly was bolted to a concrete floor. A piece of polyethylene
film was placed on the floor in the assembly before the soil was compacted.
This film was removed before the liner was mounted in the base.
36
-------
Figure 3. Jig used in compacting the specimens of soil and the other admix
materials. It was bolted to the floor during compaction. The
spacer for the soil specimens fit into this jig as assembled.
The three tampers were used in compacting this
soil-cement and bentonite clay specimens:
soil as well as the
Tamper 1: Weight 6.8 kg (15 Ib)
Face, flat square, 125 x 125 mm (5 x 5 in.)
Tamper 2: Weight 7.3 kg (16 Ib)
Face A, flat round, 50 mm diam. (2 in.)
Face B, "sheep's foot", 13 mm diam. (0.5 in.)
Tamper 3: Face, flat rectangular, 20 x 40 mm (0.75 x 1.5 in.)
Struck with 1 kg hammer (2 Ib)
Because of its plastic nature, the Mare Island soil could not be
blended with the soil-shredder. Near or above its optimum moisture con-
tent, the soil was too sticky to pass through the shredder, and, when
drier, it was too hard causing the shredder to stall. Therefore, soil for
the liners was blended by taking small scoopfuls from each bag of soil and
discarding lumps that were dry or unusually wet. Soil for each lift (1.5
to 2 in. loose, compacted to 1 to 1.25 in.) was placed in the spacer,
crushed, and leveled with Tamper 1 and compacted by repeated tamping with
Tamper 2 using alternatively the 2-in. diameter flat surface "A" and the
0.5-in. diameter "sheep's foot" face B. Final compaction of each lift was
with the "sheep's foot" face to provide a rough surface for keying to the
37
-------
next layer. The edges were compacted with Tamper 3 struck with a hammer
twice around all edges for each lift. The top layer of each liner was
leveled, after compacting, by additional tamping with Tamper 1. The
compacted soil liner is shown in Figure 4. These liners were covered
with polyethylene film and protected from drying until mounted in the
cells.
The cell bases were filled with the silica gravel leveled to support
the soil. After the liners were mounted in the cells, a ring of Epoxy 1
was cast into a triangular groove cut into the soil around the periphery of
the liner. The outside of the joint between the spacer and the cell was
sealed with butyl caulk.
Cores cut from compacted soil liners were slightly more permeable than
the cores from the water-laid deposits removed from Mare Island. Results
from measuring the permeability of cores from compacted liners are pre-
sented in Table 6.
ADMIXED LINER MATERIALS
The admixed liner materials were selected or designed to yield perme-
ability coefficients of 10~7 cm s'1 or less. The admix materials selected
for the exposure test are:
Hydraulic asphalt concrete 2.5 in. thick
Modified bentonite and sand 5.0 in. thick
Soil-cement with surface seal 4.0 in. thick
Though water permeability was the primary test in evaluating admix
materials, other tests appropriate to the specific materials were also
used. The tests used in evaluating the admix materials are discussed under
each individual material.
Sources of materials for the admix liners are shown in Appendix E.
Details regarding the individual liner materials are presented below.
Asphalt Concrete (Hydraulic)
The mix design used for the hydraulic asphalt concrete (HAC) liner
specimens called for dense-graded aggregate to 0.25 in. maximum size and 9
parts of asphalt AR-4000 per 100 aggregate. A one-half-ton batch of hy-
draulic concrete was prepared in a hot-mix plant and hauled 5 miles in an
insulated trailer to the test site. The temperature during mixing was
345°F. The hot concrete was raked into a form (10 ft x 3.5 ft x 2.25 in.)
and leveled with a wooden screed. Compaction was started when the mix had
cooled to 275°F and was performed with a gasoline-powered "Jumping Jack"
rammer having a 10 x 10 in. compacting foot. Compaction was continued for
one-half hour, at which time the HAC began to stick to the compactor foot.
The HAC was quite plastic, and some asphalt bled to the surface.
38
-------
UD
Figure 4. A compacted fine-grain soil liner specimen in 13-in. tall spacer
ready to be mounted in cell base. Also shown are the frame in
which the specimen had been compacted and bolts for holding the
assembly to the floor while the liner was compacted.
-------
TABLE 6. PERMEABILITY OF COMPACTED SOIL LINER SPECIMENS3
Coefficient of permeability,
Description of specimen cm s~l
Laboratory-prepared specimens (7 samples)^ 6.5 x 10~8 to 1.2 x 10"7
Core from specimen compacted in spacer on
cell base0
Core from "resilient" end of cell 4.5 x 10~7
Core from "firm" end of cell 1.7 x 10~7
Core from 12-in. thick specimen compacted
in spacer in jig on concrete floor (2 samples) 9.4 x 10~8 and 4.2 x 10~7
Core taken from water-laid deposits of the
soil (3 samples) 1.0 x 1Q-8 to 1.0 x 10~7
Permeabilities determined in a back pressure triaxial permeameter
(Vallerga and Hicks, 1968) with a back pressure of 1.0 atm, a con-
fining pressure of 1.3 atm, and a gradient of about 25.
bSee Table 5.
cDue to the geometry of the cell base, the shallow end of the base was
"springy," and the soil at that end rebounded during compaction.
A one-gallon sample of uncompacted HAC and a one-quart sample of the
AR-4000 asphalt (from the tank at the mixing plant) were retained for
laboratory tests. After the compacted HAC had cooled overnight, 14 two-
inch diameter cores were cut.
The tests performed on the asphalt and the concrete are listed in
Table 7 and the results are presented in Tables 8 and 9.
The water permeability of six of the cores ranged from 2.8 x 10~8 to
1.7 x 10~9 cm s'1 (Table 8). The compacted slab was cut with a diamond saw
into 11.75 x 17 in. specimens to fit in the spacers for mounting in the
cells. The consistencies of the original asphalt and extracted asphalts,
as measured by penetration values, are presented in Table 9. These data
show the hardening of the asphalt which takes place during mixing and
compaction.
Each specimen was sealed into a 3.5-in. spacer. The specimen was
first placed on a cell base which had been filled with silica gravel. A
spacer was placed around the specimen and a wax-coated metal form was
placed on top of it to form a ring. The space between the spacer, the
liner, and the base was filled with a grout consisting of Epoxy 1 (2 Part
A:l Part B:3 sand). Grout of a similar composition was used to cast the
ring above the specimen.
40
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TABLE 7. TESTING OF HYDRAULIC ASPHALT CONCRETE
Property
Test method
Original Exposed
Water permeability
Density and voids
Water swell
Compressive strength
Asphalt content
Penetration of asphalt
Viscosity of asphalt,
sliding plate
Sieve analysis of the
aggregate
Back-pressure permeameter
(Vallerga and Hicks, 1968) x
ASTM D1184 and D2041 x
California Division of
Highways 305 x
ASTM D1074 x
ASTM D1856 x
ASTM D5 x
California Division of
Highways 348 x
ASTM C136 and C117 x
x
x
X
X
X
TABLE 8. WATER PERMEABILITY OF CORES CUT FROM SLAB OF HYDRAU-
LIC ASPHALT CONCRETE COMPACTED FOR PREPARING LINER SPECIMENS9
Coefficient of
Core
5
7
12
16
17
18
Location on slab
In
In
In
In
In
In
area
area
area
area
Top si
area
area
compacted
compacted
compacted
last
last
last
compacted first
ice removed
compacted
compacted
first
first
cm s~l
6
2
2
1
<1
ca 1
.6
.8
.1
.7
.5
.7
x
x
X
X
X
X
X
10-9
10-8
10-8
10-8b
10-8
10-8b
10-9
permeabil ity
in
0
0
0
<0
0
<0
ca 0
. yr-1
.08
.34
.26
.12
.21
.19
.02
b
b
Permeabilities measured in a triaxial, back pressure permeameter
with a pressure of 1.0 atm, a confining pressure of 2.0 atm, and a
gradient of about 25.
^Because of long test runs, the specimens were removed from test
before constant values were obtained.
41
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TABLE 9. PROPERTIES AND COMPOSITION OF HYDRAULIC ASPHALT CONCRETE
Unexposed
concrete/asphalt
Property
1975/76
1983
Properties of concrete
Density, g cm"3
Ib ft-3
Voids content, % by volume
Voids ratio (vol vcids/vol solids), %
Compressive strength
Initial, psi
After 24 h immersion in water, psi
Retention of strength after immersion,
Coefficient of permeability, cm s~l
Analysis of concrete0
Asphalt extracted, %
per 100 aggregate
Sieve analysis of aggregate, % passing:
1/2 in. (12
3/8 in. (9.
1/4 in. (6.
(4.
(2.
No. 4
No. 8
No. 16 (1.
No. 30 (0.
No. 50 (0.
No. 100 (0.
No. 200 (-0.
.5 mm)
5 mm)
3 mm)
75 mm)
36 mm)
18 mm)
60 mm)
30 mm)
15 mm)
075 mm)
Soluble in hydrochloric acidd, %
Rock, >No. 8 (>2.36 mm)
Sand, No. 8 to No. 200 {0.075 to 2.36 mm)
Silt,
-------
The HAC liner specimens in the spacers were mounted in the cells and
were tested with water prior to adding wastes (Figure 5). Five were found
to leak between the spacer and the epoxy seal, probably the result of
differences in thermal coefficients of the steel and the asphalt concrete.
Five of the asphalt concrete specimen-spacer combinations were chilled and
the steel spacers were removed. The surfaces of the original epoxy seal
were roughened and the new spacers of epoxy resin-aggregate mix were cast
around and on top of the epoxy seal. This was done through the use of a
wax-coated steel form and a wooden outer form. The cast epoxy spacers
consisted of Epoxy 2 filled with sand (2 Part A:l Part B:4.5 sandblasting
sand) with a thin-layer of unfilled Epoxy 3 poured on top to form a level
surface. Neoprene sponge gaskets were used to seal the joints between the
spacers and exposure cell tanks as in all the other cells.
Figure 5. Leak-testing of hydraulic asphalt concrete.
with water and the base pressurized.
Bentonite-Sand Admixes
Specimen is covered
Bentonite is a colloidal clay composed chiefly of the clay mineral
smectite (montmorillonite). Two major varieties of bentonite that have
commercial application are: (1) sodium bentonite, which has a high swel-
ling capacity in water, and (2) calcium bentonite which has a negligible
swelling capacity. Because of its high swelling capacity, sodium bentonite
43
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is used as a sealant or a lining material for water storage and conveyance.
Polymer-modified bentonites have been developed, the suppliers of which
have claimed improved resistance to salt contamination and to other
contaminants aggressive to bentonites.
Bentonite is commercially available in bags or in bulk as a fine powder
or as granules. When used as a lining material, it is either applied
directly, or mixed into sand or the top layer of soil and compacted. In
either case, the layer containing bentonite is generally covered with a
protective soil cover. Slurry trenches, filled with soil-bentonite slurry,
are used to control lateral movement of water or liquid wastes. Compacted
soil-bentonite or sand-bentonite liners are often 4 to 6-inches thick.
Selection
Two polymer-modified sodium bentonites were included in the study.
The materials are hereafter referred to as Bentonite A and Bentonite B.
Laboratory specimens were prepared with 6%, 12%, and 20% of each treated
bentonite in a well-graded sand, and briquets were compacted with various
water contents to determine optimum moisture content for compaction to
maximum density. Sieve analysis of the sand used was:
Sieve size
Mesh Opening, ym % Passing
8 2360 96
16 1180 80
30 600 50
50 300 15
200 75 2.6
As the sand-bentonite compositions were not strong enough to be tested
without support, specimens at the optimum moisture content were compacted
in brass tubes for testing in the back-pressure permeameter. Permeability
coefficients were in the range of 10"? to 10~^ cm s~l, as shown in Table
10.
TABLE 10. WATER PERMEABILITY OF LABORATORY COMPACTED
MODIFIED BENTONITE-SAND SPECIMENS
Composition Coefficient of permeability, cm s~l
Modified
Sand Water bentonite Bentonite A Bentonite B
94
88
80
12
12
12
6
12
20
5
7
8
.0
.4
.0
X
X
X
10-7
10-9
10-10
7
2
3
.1
.8
.5
X
X
X
10-8
10-9
10-9
44
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Preparation of Polymer-Modified Bentonite-Sand Liner Specimens--
The liner specimens of polymer-modified bentonite were compacted in
the 7-in. high spacers. Each spacer was placed on a cell base previously
coated with Epoxy 2; the outer flange of the base was slightly roughened
with sandpaper to ensure good adhesion of the epoxy seal to the epoxy
coating. Masking tape was pressed around the flange between spacer and
base, and a wax-coated metal form was placed on the base inside the spacer.
Between the form and the spacer, an epoxy seal (approximately 0.5 in. high
by 1 in. wide) was cast of grout made with Epoxy 2 and sandblasting sand.
After the seal was cured and the form removed, the base was filled with
crushed silica gravel to the level of the bottom of the seal. The gravel
was covered with woven glass fabric and the wooden reinforcing frame
was bolted around the spacer. The treated bentonite-sand mixtures were
compacted in the spacer following the same procedure and with the same
tampers used in compacting the fine-grain soil.
Eight liner specimens were fabricated of 12% Bentonite B and 88%
well-graded sand, mixed at optimum moisture content and compacted in the
liners already sealed to bases. For each liner, 53.5 Ib of sand containing
3% water was mixed in a mortar boat with 5.5 pounds more water and with 7.1
Ib Bentonite B. This mixture was placed in the prepared spacer in 1-in.
lifts, and each lift was compacted with tampers. The compacting effort was
less than that used for the native soil and soil cement liners in order to
avoid damage to the epoxy seal between the spacer and the base. Two liner
specimens were fabricated in the spacers of 20% Bentonite A and 80% well-
graded sand mixed at 3% water content. The compacted Bentonite B liners
were 5-in. thick and the dry-tamped Bentonite A liners 4-in. thick.
Both were expected to be about 6-in. thick after complete hydration.
Two gallons of tap water was added on each liner through a perforated
can to avoid displacing the tamped sand-clay mixtures. After one day,
thickness increased from 4.0 to 4.5 in. and after one week to 4.75 in. One
week was allowed for "fresh-water hydration" in accordance with the manu-
facturers' recommendations before draining the excess water and adding
wastes. A sealing ring of Epoxy 2 grout was cast around the top edge of
each of the compacted specimens. The average actual thickness after
complete hydration was 5.2 in. for the Bentonite A liners and 5.5 in. for
the Bentonite B liners.
Soil-Cement
Selection of Soil--
Most of the fine-grain soils being considered for use as compacted
native soil liners were evaluated in soil-cement mixes. Formulations
containing various proportions of soil:portland cement:water were molded
into briquets, cured, and tested in the back-pressure permeameter. The
lowest permeability was obtained with soil-cement based on "waste fines"
from a local quarry, with 12 parts of Type 5 (sulfate-resistant) portland
cement per 100 parts of soil, and 12% of water on the total of soil plus
cement (Table 11). The "waste fines" material is available in large
45
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TABLE 11. WATER PERMEABILITY OF SOIL-CEMENT SPECIMENS^
Soil
Tennis court
Tennis court
Tennis court
"Mudjacki
"Mudjacki
"Mudjacki
Graywacke
Graywacke
Graywacke
Core from
pacted in
base
ng"
ng"
ng"
fi
fi
fi
cl
cl
cl
cl
cl
cl
nes
nes
nes
speci
Type V
cement,
parts per
100 g
dry soil
ay
ay
ay
ay
ay
ay
soil
soil
soil
men com-
8
10
12
8
10
12
10
12
10C
Water,
parts per
100 g Coefficient of
dry soil
10
10
10
12
12
12
13
12
12
cm s"l
1
1
5
3
5
6
1
1
2
4
.6
.3
.1
.4
.3
.5
.9
.5
.9
.0
X
X
X
X
X
X
X
X
X
X
10-6
10-6
10-6
10-6
10-6
10-6
10-6
10-?b
10-7d
10-7e
permeability
in. yr"l
20
16
63
42
66
81
24
1.9b
3.6
5.0
spacer in cell
12
13.4
5
.7
X
ID-0
0.71
aExcept where otherwise noted, permeabilities determined in a back pres-
sure permeameter with a confining pressure of 2.0 atm for all specimens
except those made with "mudjacking" clay (1.3 atm confining pressure), a
back pressure of 1.0 atm, and a gradient of approximately 25.
^Average of measurements with back pressures ranging from 1.0 to 3.0 atm.
cRice hull ash cement (an acid-resistant pozzolanic cement).
^Average of measurement of back pressures ranging from 2.0 to 4.0 atm.
eRepeat with back pressure of 1.0 atm.
quantities as a by-product of the washing of crushed graywacke and has been
used as a compacted soil cover over a chemical waste dump. Sieve analysis
(wash) of the soil was:
Sieve size
Mesh Opening, ym
50
100
200
325
300
150
75
45
% Passing
98
93
83
70
46
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The graywacke fines soil was received mostly in large friable lumps
that were broken up by passing the soil twice through a shredder to yield
a thorough blend with maximum agglomerate size of approximately 0.125 in.
(3 mm). The soil was air-dried on a concrete slab then stored indoors
until used.
Preparation of Compacted Soil-Cement Liners
The soil-cement specimens were compacted in 5-in. high spacers, the
inner surfaces of which were coated with epoxy and sand. The compaction
procedure was the same as used with the fine-grain soil; the spacer was
placed within a supporting wood frame (Figure 6) to prevent bulging of the
sides and the frame and spacer were bolted on a concrete floor. A piece of
polyethylene film was placed on the concrete floor at the bottom of the
spacer.
Figure 6. Compaction of a soil-cement liner specimen with Tamper 1 is
shown as is the character of the uncompacted soil-cement.
47
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For each liner, 50 Ib of dry soil was thoroughly mixed in a mortar
boat with 6 Ib of Type 1-2-5 port!and cement, then with 6.7 Ib of tap
water. The mixed soil-cement was crumbly and barely damp before com-
paction. One-inch lifts were placed in the spacer and compacted with
Tampers 1, 2, and 3, described previously. Figure 6 shows the compaction
of the soil-cement with Tamper 1. Final compaction of each lift was with
the "sheep's foot" Face B of Tamper 2, to provide a rough surface for
keying to the next lift. The edges were compacted with Tamper 3, twice
around all edges for each lift. After a total compacted thickness of 4 in.
was obtained, the top surface was leveled by additional tamping with
Tamper 1. The compacted soil-cement was quite firm, but plastic enough to
be compacted without cracking or shattering. The thickness of the com-
pacted liner specimens was 3.75 to 4.0 inches. One-half gallon of water
was poured on the surface and the soil-cement was cured for at least
7 days.
The surfaces of the cured liners were allowed to dry sufficiently to
provide good adhesion for 1) an epoxy ring cast around the periphery of the
liner, 2) sealing the liner to the spacer, and 3) application of two
coal-tar modified epoxy surface sealing coatings to portions of the liner
surfaces. After the epoxies cured, the liners were again flooded with
water until they were filled with wastes. Each spacer was mounted on a
cell base which had been filled with crushed silica gravel leveled to
support the liner. Neoprene sponge gaskets were used to form seals between
the flanges of the spacers and the cell tanks. The cell base, the spacer
with sealed-in liner specimen, and the exposure tank were bolted together,
and a bead of butyl caulk was applied to the outside of the base-to-spacer
junction to make it airtight.
Application of Surface-Sealing Coatings--
Two sections of each soil-cement liner were coated with two coal-tar
epoxy resin sealers. Seal-coats have been applied to soil-cement pond
liners to increase strength, to increase resistance to wastes, and to
reduce permeability. However, any settling and cracking in a soil-cement
liner of a waste pond results in the cracking of the seal-coat. Prelimi-
nary tests indicated that both coatings under test were relatively brittle.
A crack in the seal-coat would allow the waste to begin to attack the
possibly weak interface of the seal-coat and the soil-cement. The exposed
seal-coat edge on the soil-cement test liners would show if this interface
was susceptible to attack. These two sealers and the primer used for one
of them were two-component systems. Each was mixed according to the
manufacturer's directions and applied by brush. The areas coated were
6-in. square, located at one end of the cell, as shown in Figure 7.
Coating K consisted of 3 coats of a proprietary epoxy bituminous
coating. The first coat was diluted, 2 parts resin and 1 part thinner,
according to manufacturer's instructions; the average total thickness was
0.044 in. Coating C consisted of 1 coat of primer, 0.007-in. thick, plus 2
coats of a second proprietary epoxy coal-tar coating, 0.018-in. thick, for
a total thickness of 0.025 in.
48
-------
Coating K
Coating C
Uncoated
Figure 7. Pattern used in coating the soil-cement.
SPRAYED-ON ASPHALT MEMBRANE
Specimens of emulsified asphalt applied on a nonwoven polypropylene
fabric mat were furnished by the supplier in 18 x 24 in. sheets, 0.3-in.
thick, with a seam running across the width at the center. These sheets
were cut to a size which would fit loosely inside the 1.25-in. spacer.
When mounting this liner, the cut sheet was placed on a base filled
with crushed silica gravel; the spacer was placed around the liner, and an
epoxy ring was cast around the inside of the spacer. The epoxy resin was
spread on, around, and slightly under the edge of the liner. This ring of
epoxy seals the liner to the base and the spacer, so that waste cannot
by-pass the liner. The epoxy ring was a grout consisting of sand-filled
epoxy resin (Epoxy 1:2 Part A:l Part B:3 sand, and 2% thixotropic agent).
The assembled cells were leak tested by filling with water; none of the
seals leaked.
Properties of the asphalt sheet and of the extracted asphalt are
presented in Table 12.
TABLE 12. PROPERTIES OF EMULSIFIED ASPHALT MEMBRANES
Property
Value
Moisture content of liner, % 0.26
Moisture vapor transmission, metric perm cm 6.7 x 10~2
Viscosity3 of extracted asphalt at 25°C, mP:
At shear rate of 0.05 s"1 6.1
At shear rate of 0.01 s'1 5.9
At shear rate of 0.001 s'1 5.7
Shear susceptibility -0.02
Penetration at 25°C (calculated from viscosity) 41
Sliding Dlate viscometer.
49
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POLYMERIC MEMBRANE LINERS
When this project was initiated in 1975, flexible polymeric membranes
were assuming increased importance as liner materials because of their very
low permeability to water and other fluids. Polymeric membranes had been
successfully used for the lining of water conservation and conveyance
structures since about 1958; consequently, there was considerable interest
in the use of such materials for the lining of waste storage and disposal
facilities.
Polymeric membrane liner technology was then and remains (in 1983)
relatively new, particularly with its application to waste containment.
The current state of liner technology is described in the EPA Technical
Resource Document, SW-870 (Haxo et al, 1983). The polymeric membrane liner
materials vary considerably in polymer types, physical and chemical pro-
perties, methods of installation, costs, and interaction with various
wastes. Not only are there differences among the polymers used, but also
there are considerable variations in the lining materials of a given
polymer type due to compound formulation, construction, and manufacturing
differences among the producers.
Polymers used in the manufacture of lining materials include a wide
range of rubbers and plastics differing in basic characteristics, e.g.
chemical composition, polarity, chemical resistance, and crystallinity.
They can be classified into four types:
- Rubbers (elastomers) which are vulcanized, i.e crosslinked (XL).
- Thermoplastic elastomers, which do not need to be vulcanized (TP).
- Thermoplastics which are generally unvulcanized (TP), such as PVC.
- Thermoplastics which have a relatively high crystalline (CX) con-
tent, such as the polyolefins.
Table 13 lists the various types of polymers that are used and indi-
cates whether they are used as a thermoplastic, partially crystalline,
nonvulcanized or vulcanized compound and whether fabric is used to rein-
force lining materials manufactured with them. The polymeric materials
most frequently used in liners at the time this project was undertaken were
polyvinyl chloride (PVC), chlorosulfonated polyethylene (CSPE), chlorinated
polyethylene (CPE), butyl rubber (IIR), ethylene propylene rubber (EPDM),
and neoprene (CR). The thickness of polymeric membranes for liners has
ranged from 20 to 80 mils, with most in the 20- to 60-mil range.
Note: Subsequently, liners based on high-density polyethylene
(HOPE) were introduced and are being used in lining land
storage and disposal facilities.
Most polymeric lining materials are based on single polymers and gen-
erally are compounded with fillers, antidegradants, plasticizers, and if
crosslinking is needed, curatives. Compounds based on the same polymer can
50
-------
TABLE 13. POLYMERS CURRENTLY (1983) USED IN MEMBRANE LINER MANUFACTURE
Polymer
Abbrevi- Type of
ation compound9
Fabric
reinforcement
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
IIR
CPE
CSPE
XL
TP and XL
TP and XL
With and without
fabric
Usually without
fabric
Usually with
Elasticized polyolefin ELPO TP (CX)
Elasticized polyvinyl chloride EPVC TP
Epichlorohydrin rubber ECO XL
Ethylene propylene rubber EPDM XL and TP
Neoprene (chloroprene rubber) CR XL
Nitrile rubber NBR TP and XL
Polyethylene
- High density HOPE CX
- Low density LDPE CX
Polyvinyl chloride PVC TP
fabric
None used
Usually with
fabric
With and without
fabric
Usually without
fabric
Usually without
fabric
With and without
fabric
None used
None used
Usually without
fabric
aCX = crystalline, TP = thermoplastic, XL = crosslinked.
vary considerably in composition from manufacturer to manufacturer. Blends
of two or more polymers, e.g. plastic-rubber alloys, are being developed
and used in liners. Consequently, it is becoming difficult to make generic
classifications based on individual polymers, although one polymer will
generally predominate in the compound. Blending of polymers introduces
the long-range possibility of the need for performance specifications.
However, long-term liner performance in the field cannot, at the present
time, be completely defined by current laboratory tests.
Most of the membrane liners currently manufactured are based on
unvulcanized or uncrosslinked polymeric compounds and thus are thermo-
plastic. Even though a compound may be more chemically resistant once
vulcanized, such as is the case with CPE and CSPE compounds, the lining
material has been supplied unvulcanized because it is easier to seam and
51
-------
repair such a liner in the field. Noncrystalline, thermoplastic polymer
compositions can be heat-sealed or seamed with solvent or bodied solvent (a
solvent containing dissolved polymer to increase the viscosity and reduce
the rate of evaporation). Semicrystal1ine sheetings, which are also
thermoplastic, can only be seamed by thermal or fusion methods. Informa-
tion on individual polymers and liners is presented in subsequent sub-
sections. Subjects covered on each polymer are: composition, general
properties and characteristics, general use, and specific use in liners.
In 1975, when making the selection of specific membrane materials for
exposure tests, the following considerations served as guidelines:
1. To include a broad representation of polymer types because of
the great diversity in the composition of wastes that may be
impounded.
2. To include several polymeric membranes that were under investiga-
tion for resistance to MSW leachate (Haxo et al, 1982) which
offered promise as liners for use in impounding hazardous wastes
and allowed an intensive study of the characteristics of a few
liners.
3. To exposure test liners of equal thickness. Most of the liners
were available in 30-mil thickness; however, if this thickness was
not available in the specific polymer type, then the thickness
normally manufactured was used.
4. To test primarily the effect upon the barrier compound, that is,
to test sheetings that were not reinforced with fabric.
In making the selection it was not possible to obtain liners from
all liner producers, nor was it possible to obtain unreinforced samples of
all polymer types. Representative liners of the different types were
selected from those that were available. If several membranes of a given
polymer were available, the membrane exhibiting the best physical proper-
ties was generally selected. Specific combinations of membranes and wastes
were selected after preliminary screening tests which are described in
Section 6.
Selection of Polymeric Membranes for Exposure Testing
The specific polymer types selected for the primary exposure in this
study are listed in Table 14 and are discussed below in alphabetical order
along with several other polymers that were tested in other exposures.
Detailed data on the properties of these materials are given in Appendixes
F and G.
Since 1975 there have been important developments in liner technology
which led to the introduction of new polymeric compositions, compounds, and
constructions into the market. The most important of these developments
are included in the discussion below.
52
-------
Butyl Rubber (IIR)«
Butyl rubber is a copolymer of isobutylene and a small amount of iso-
prene (2-5%) introduced in the polymer chain to furnish sites for vulcani-
zation (crosslinking). Properties of butyl rubber vulcanizates that relate
to their use as a liner are:
- Low gas and water vapor permeability.
- Thermal stability.
- Ozone and weathering resistance.
- Chemical and moisture resistance.
- Resistance to animal and vegetable oils and fats.
Butyl rubber is compounded with fillers and oil and generally vul-
canized with sulfur. Some recent butyl compounds contain minor amounts of
EPDM to improve ozone resistance. Butyl vulcanizates are highly swollen by
hydrocarbon solvents and petroleum oils, but are only slightly affected by
TABLE 14. PRIMARY POLYMERIC MEMBRANE LINERS EXPOSED IN CELLS
Polymer
Butyl rubber (IIR), fabric-
reinforced
Chlorinated polyethylene
(CPE)
Chlorosulfonated polyethy-
lene (CSPE), fabric-
reinforced
Elasticized polyolefin (ELPO)
Liner
number^
57R
77
6R
36
Thickness3,
mi 1
34
32
34
22
Type of
compound0
XL
TP
TP
CX
Ethylene propylene rubber
(EPDM) 26 50 XL
Neoprene (CR), fabric-
rei nforced
Polyester elastomer (PEEL)
Polyvinyl chloride (PVC)
43R
75
59
32
8
30
XL
TP
TP
3Nominal thickness.
^Matrecon serial number assigned to membrane liner material when
received; R = fabric-reinforced.
CXL = Crosslinked or vulcanized; TP = thermoplastic; CX = parti-
ally crystalline.
53
-------
oxygenated solvents and other polar liquids. Butyl vulcanizates also have
a high resistance to mineral acids and a high tolerance for extremes in
temperature, and retain their flexibility throughout their service lives.
Liners of butyl rubber were among the first synthetic liners to be
used (Dedrick, 1980; Lauritzen, 1967; Smith, 1980). As of 1975, butyl
rubber liners had been in service for about 25 years in water impoundments.
In outdoor exposure in water management use, butyl rubber sheetings have
generally shown little or no degradation after 20 years of service. These
sheetings are generally seamed with two-part, low temperature curing
adhesives which, primarily because of their lower degree of ultimate
cross linking, may be less resistant to the service conditions than the
liner itself.
The particular butyl rubber sheeting selected for exposure in the
primary exposure cells was vulcanized, had a thickness of 34 mil, and was
reinforced with a nylon fabric of 22 x 11 ends per inch thread count. A
second butyl sheeting of 62 mil, with no fabric reinforcement, was also
selected for exposure in immersion tests.
Chlorinated Polyethylene (CPE)--
Chlorinated polyethylenes form a family of flexible thermoplastic
polymers produced by chlorinating high-density polyethylene and, as such,
they are saturated polymers with good aging and chemical resistance. In
1975, when this study was initiated, CPE liners had only recently been
developed. CPE can be crosslinked with peroxides, but in membrane liners
uncrosslinked thermoplastic compositions are generally used. CPE is
compounded with fillers, such as carbon black and inorganic fillers, and
with plasticizers. Membranes of CPE are seamed thermally with solvent
adhesives or by solvent welding.
Mote: In recent compounding practice, polyvinyl chloride or
CSPE are sometimes added to improve tensile and thermal
properties.
Most CPE compositions withstand ozone, weathering, and ultraviolet
light, and resist many corrosive chemicals, hydrocarbons (if crosslinked),
microbiological attack and burning. Also, some compounds of CPE are
serviceable at low temperatures and are nonvolatile. As of 1975, sheetings
of CPE had been used as linings for water reservoirs and for pits and ponds
for storage of waste waters and chemicals.
The CPE membrane selected for the primary exposure and other exposure
tests was a thermoplastic of 30 mil nominal thickness, and was not rein-
forced with fabric. Two other CPE sheetings were included in the study in
immersion and other tests; one was a thermoplastic of 22-mil thickness and
the other was a vulcanized sheeting of 36-mil thickness.
54
-------
Chlorosulfonated Polyethylene (CSPE)--
Chlorosulfonated polyethylenes form a family of saturated (no double
bonds in the polymer chain) polymers prepared by treating polyethylene in
solution with a mixture of chlorine and sulfur dioxide. These polymers
contain from 25-43% chlorine and from 1.0-1.4% sulfur and can be used
in both thermoplastic (uncrosslinked) and in vulcanized (crosslinked)
compositions.
Most CSPE compositions are characterized by ozone resistance, light
stability, heat resistance, good weatherability, and resistance to deteri-
oration by corrosive chemicals, e.g., acids and alkalies. They have good
resistance to growth of mold, mildew, fungus, and bacteria, but only
moderate resistance to oil. Membrane liners based on this type of polymer
are available in both vulcanized and thermoplastic forms, but primarily in
the latter. The thermoplastic versions slowly crosslink on exposure to
moisture and the weather after placement. Usually CSPE sheetings are
reinforced with a polyester or nylon scrim. They generally contain at
least 45% of CSPE polymer by weight (Burke, 1979; Du Pont, 1973). The
fabric reinforcement gives needed tear strength and dimensional stability
to the sheeting for use on slopes; it reduces the distortion resulting from
shrinkage when placed on the base and when exposed to the heat of the
sun.
CSPE membranes can be seamed by heat sealing, dielectric heat sealing,
solvent welding, or by using a "bodied" solvent adhesive. As of 1975, they
had been used to line pits, ponds, and lagoons, and also to impound highly
acid-contaminated fluids. After PVC membranes, CSPE membranes were the
most widely used of the polymeric flexible liner materials.
The specific CSPE sheeting selected as the primary liner material for
this study was a fabric reinforced nylon sheeting of 8 x 8 epi thread count
and a thickness of 34 mils. It had been previously used as the primary
CSPE liner in a study of liner materials in contact with MSW leachate (Haxo
et al, 1982). Three additional CSPE sheetings were incorporated in the
exposure test program. Two unreinforced sheetings were exposed in im-
mersion and pouch tests and the third, a fabric-reinforced sheeting, was
exposed as a primary liner specimen for two cells set up for immersion
tests.
Note: None of the sheetings in the program was industrial grade;
sheetings of this type were commercially introduced after
this program was well underway. Industrial grade CSPE has
greater chemical resistance than the general purpose
potable grade.
Elasticized Polyolefin (ELPO)--
Elasticized polyolefin (ELPO) is a blend of rubbery and crystalline
polyolefins. This polymeric material was introduced in 1975 as a black
unvulcanized, thermoplastic liner, which is heat scalable with a specially
designed heat welder for use both in the field and in the factory. ELPO
55
-------
has a low density (0.92) and is relatively resistant to weathering,
alkalies, and acids (Haxo et al, 1977). Sheeting of ELPO is manufactured
by blow extrusion and is supplied unreinforced, 20-mil thick, 20-ft wide,
and up to 200-ft long. It can be fabricated into panels in the factory or
shipped in rolls to a site for assembly on the field.
This material was selected as a primary liner in the test program
because of its good aging, and moisture and chemical resistance. The
specific sheeting used in this study was of 22-mil thickness. It was also
studied in immersion, tub, rack, and pouch tests.
Ethylene Propylene Rubber (EPDM)
EPDM, which was first produced commercially in 1962, is a terpolymer
of ethylene, propylene, and a diene monomer that introduces a small number
of double bonds into the polymer molecule which are sites for vulcanization
of the rubber. The unsaturation is in the side chains of the polymer and
not in the main chain, as in the case of butyl rubber. Such a location of
unsaturation imparts good ozone, chemical, and aging resistance to the
rubber.
Note: EPDM is chemically similar to, and can be covulcanized
with, butyl rubber; consequently, it is now added to
butyl rubber liner compounds to improve the resistance
to oxidation, ozone, and weathering (Matrecon, 1983).
As it is a wholly hydrocarbon rubber like butyl, EPDM when properly
compounded has excellent resistance to water absorption and permeation but
has relatively poor resistance to hydrocarbons. EPDM sheeting is available
in 54-in. widths and 20- to 60-mil thickness, in both unsupported and
fabric-reinforced versions. Special attention is required in seaming
cross!inked sheeting because low-temperature vulcanizing adhesives gen-
erally need to be used. Sheetings have also been manufactured with unvul-
canized EPDM compounds. These are thermoplastic and can be seamed with
solvent adhesives and by thermal methods.
The EPDM sheeting exposed in the primary cell was a crosslinked
unreinforced membrane of 30-mil thickness. It was also subjected to
roof exposure. In addition, three other different EPDM sheetings were
subjected to immersion and weather exposure testing; two of these were
crosslinked compositions and one was a thermoplastic version which was
reinforced with a polyester fabric of 8 x 8 epi thread count.
Neoprene (CR)
Neoprene is the generic name of a family of synthetic rubbers based
upon chloroprene. Neoprene was first introduced in 1932 and thus was one
of the first commercial synthetic rubbers. These rubbers are vulcanizable,
usually with metal oxides, e.g. MgO, ZnO, and PbO, but also with sulfur.
They closely parallel natural rubber in mechanical properties, e.g.,
flexibility and strength. However, neoprene compositions are generally
superior to natural rubber compositions in their resistance to oils,
56
-------
weathering, ozone, and ultraviolet radiation. Most neoprene sheetings are
relatively resistant to puncture, abrasion, and mechanical damage. Neo-
prene membranes have been used primarily for the containment of wastewater
and other liquids containing traces of hydrocarbons. They also give
satisfactory service with certain combinations of oils and acids (Lee,
1974). Neoprene membrane liners are vulcanized; therefore, special at-
tention is required in seaming because vulcanizing cements and adhesives
generally need to be used.
The neoprene exposed as a liner specimen in the primary cell was an
unreinforced, crosslinked sheeting of a nominal thickness of 31.25 mils.
Two additional neoprene sheetings were exposed in this study in immersion
and water tests. All were vulcanized and had no fabric reinforcement.
Polybutylene (PB)--
Polybutylene is a high molecular weight polymer synthesized from bu-
tene-1. It was introduced commercially in the United States in the early
1970's and found its major use in plastic pipe. The version of polybuty-
lene used in this project was specifically designed for blown film ex-
trusion. Films of this material feature good flexibility, heat seal-
ability, low moisture vapor transmission, and good creep resistance.
Polybutylene is available in thin films, principally for use as
packaging. It has not been manufactured for use as a liner material
although there is current interest in it for this use. Polybutylene film
was successfully used in making leachate collection bags to use in the
study of liners in contact with MSW leachate (Haxo et al, 1982).
Polybutylene was not selected as a primary liner in the exposure
cells. It was tested in pouches and used as leachate collection bags. The
film first used in this study was unpigmented, i.e. contained no carbon
black, and had a thickness of 8 mils. Later, the bags and pouches were
fabricated from black-pigmented polybutylene which had a thickness of
6 mils.
Polyester Elastomer (PEL)--
Polyester elastomers form a family of polyether esters which are
semi crystal line and thermoplastic. They were introduced commercially in
1972 and feature oil, fuel, and chemical resistance. An experimental
sheeting based on this type of polymer was available in 1975 and, because
it had oil and chemical resistance, it was selected as a primary material
for study and exposure in this program. This sheeting was unreinforced and
7-mils thickness, which made it the thinnest sheeting in the program.
Note: New versions, both of the polymer and of the sheeting, are
now available. The sheetings are thicker and reported to
be more durable than the one we used in this study.
57
-------
Polyethylene (PE)
Polyethylenes are thermoplastic crystalline polymers based upon
ethylene. They are currently made in three major types:
1. Low-density polyethylene (LDPE).
2. Linear low-density polyethylene (LLDPE).
3. High-density polyethylene (HOPE).
The properties of a polyethylene are largely dependent upon molecular
weight, crystallinity, and density. Of the three types, high-density
polyethylene polymers exhibit the greatest resistance to oils, solvents,
and permeation by water vapor and gases. Unpigmented clear polyethylene
degrades readily on outdoor exposure, but the addition of 2 to 3% carbon
black can produce ultraviolet protection. Polyethylenes, as generally
used, are free of additives such as plasticizers and fillers.
LDPE and HOPE types of polyethylene have been used as liners. Non-
fabric-reinforced membranes of low-density polyethylene have been used for
25 to 30 years (Hickey, 1969) in lining canals and ponds. The low-density
polyethylene (LDPE) available in thin sheeting tends to be difficult to
handle and to field seam. Also, it is easily punctured under impact such
as when rocks are dropped on the lining; however, it has good puncture
resistance when buried. Linings of high-density polyethylene (HOPE), which
were introduced in the USA after this project was underway, are available
in sheetings of 20- to 120-mils thickness; special seaming equipment has
been developed for making seams of these sheetings both in the factory and
in the field. This type of liner is stiff compared to most of the other
membranes described. A lining material based on linear-low-density
polyethylene (LLDPE), a recently developed version of polyethylene, was
introduced in 1982 in 20- and 30-mil thicknesses.
At the time this project was initiated, only LDPE sheeting had been
used in the USA as a lining material, and it was available as a thin film
at a thickness of about 10 mils. In the study of lining materials for
municipal solid waste landfills (Haxo et al, 1982), we found this film to
be deficient in puncture, crease, and fold resistances and not satisfactory
for impounding hazardous wastes in spite of its good chemical resistance.
Consequently, LDPE was not selected for exposure as a primary liner.
However, it was tested in pouches, and unpigmented sheeting of 31-mil
thickness in immersion tests.
Though HOPE lining material was not available in the USA at the time
this project was initiated, an unpigmented HOPE sheeting of 32-mil thick-
ness was tested in immersion tests because of the known chemical resistance
of this type of polymer. Neither of the polyethylenes that were tested
were specifically commercial lining materials.
58
-------
Polypropylene (PP)--
Polypropylene is a partially crystalline thermoplastic polymer based
on propylene. It is quite hard, stiff, has good chemical resistance, and
has potential as a membrane liner as indicated by its recent commercial
introduction in Europe.
The specific polypropylene sheeting assessed in this program was an
unpigmented, 33-mil sheeting which was immersion tested in 13 wastes or
liquid test media. It was not tested as a primary liner.
Polyvinyl Chloride (PVC)--
Polyvinyl chloride is produced by any of several polymerization
processes from vinyl chloride monomer (VCM). It is a versatile thermo-
plastic, which is compounded with plasticizers and other modifiers to
produce sheetings having a wide range of physical properties. Polymeric
membranes based upon PVC are the most widely used flexible liners.
PVC sheeting is produced in roll form in various widths up to 96-in.
and thicknesses of 20 to 30 mils. Most liners are used as unreinforced
sheeting, but fabric reinforcement has been used. PVC compounds contain
25% to 35% of one or more plasticizers to make the sheeting flexible and
rubber-like. They also contain 1% to 5% of a chemical stabilizer and
various amounts of other additives; PVC compounds should not contain any
water soluble ingredients. A wide choice of plasticizers can be used in
PVC sheeting, depending upon the application and service conditions under
which the PVC compound is to be used. Both monomeric plasticizers, such as
phthalate esters, and polymeric plasticizers, such as resins, are used with
PVC. Plasticizer loss during service is a source of PVC liner deteriora-
tion. There are three basic mechanisms for plasticizer loss: volatiliza-
tion, extraction, and microbiological attack. The use of the proper
plasticizers and an effective biocide can virtually eliminate microbio-
logical attack and minimize volatility and extraction. The PVC polymer,
itself, is generally not affected by service in buried conditions. It is
affected, however, by exposure to ultraviolet light.
PVC sheetings can deteriorate relatively quickly on exposure to
weather due to wind, sunlight, and heat, which cause polymer degradation
and loss of plasticizer; consequently, when used as liners they are gen-
erally covered with soil. Plasticized PVC sheetings are quite resistant to
puncture and relatively easy to seam by "welding" with solvents or bodied
solvents, adhesives, and heat.
The PVC membrane selected for testing in the primary cells was an
unreinforced sheeting of 33-mil thickness. It was tested in six different
wastes in the primary cells and in 12 wastes in immersion. Seven addi-
tional PVC sheetings were exposure tested in immersion and pouch tests.
All were unreinforced and ranged in thickness from 11 to 33 mils. All
eight were also tested in the project on liners for MSW leachate (Haxo et
al, 1982). In order to furnish tanks for immersion testing, two cells were
lined with an unreinforced sheeting of 20-mil thickness.
59
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Testing of Polymeric Membranes
The testing of a polymeric membrane liner before exposure charac-
terizes the specific sheeting and furnishes a baseline for assessing the
effects of exposure. Measurement of the same properties during or after
exposure to a given environment can be a measure of the effect of the
exposure. For many plastic and rubber products there are limits in the
changes that can take place in various properties beyond which the product
is not serviceable or is likely to fail. At the time this project was
started and even continuing to the present time (1983), no such criteria
exist for membrane liners. Establishment of such criteria must await
results of field performance which will require extended exposure of
membranes in service. Measurement of the changes in properties in labora-
tory and field exposures will yield information as to the compatibility of
the liner and the waste liquid which can be useful in selecting liner
materials that will perform satisfactorily in a given waste environment.
It is important, therefore, to choose the important properties to follow in
an exposure study.
Polymeric membranes are tested by a variety of methods which depend
upon the type of membrane liner. Sheetings used as liners have been
developed by three different industries, i.e. rubber, plastics, and tex-
tile. Each has developed standard test methods. Some test methods for one
type of sheeting are not appropriate for other types; for instance, using a
dumbbell with a 1/4-in. restricted area, such as is used in the testing of
rubber vulcanizates, is not as satisfactory for measuring for specification
purposes the tensile properties of fabric-reinforced materials as a 1-in.
wide strip or a grab tensile specimen.
Note: As we were assessing the effects of exposure on the
barrier coating of the membrane, the dumbbell was used and
appeared satisfactory because the thread count was not
greater than 10 x 10 epi. This is discussed in Section 6.
The testing of materials, particularly with reference to polymeric
membranes for the lining of waste disposal facilities, is described by Haxo
(1981) and Haxo, et al (1983).
From the viewpoint of testing, there are four basically different
types of polymeric membranes:
- Membranes based on crosslinked elastomers without fabric reinforce-
ment.
- Membranes based on thermoplastics or uncrosslinked polymers without
fabric reinforcement.
- Membranes based on fabric-reinforced sheetings which can be based
upon either crosslinked or thermoplastic polymers.
- Membranes based on semi crystal line polymers without fabric reinforce-
ment.
60
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The methods used for testing polymeric lining materials can be grouped
into four categories:
- Analyses to assess composition and to fingerprint the membrane.
- Tests of physical properties, including information regarding con-
struction and dimensions of the membrane.
- Tests to determine properties in stress environments and aging tests
in specific exposures or compatibility tests.
- Tests of durability of lining materials under conditions that
simulate actual field service.
These tests can include measurements of the following properties:
- Analytical properties before and after exposure to different
environments:
- Ash.
- Extractables.
- Specific gravity.
- Volatiles.
- Physical properties before and after exposure to different environ-
ments:
- Dimensional stability of immersion specimens (before and
after).
- Hardness (before and after).
- Modulus of elasticity of crystalline membranes (before and
after exposure).
- Ply adhesion in fabric-reinforced sheeting (before and
after exposure).
- Puncture resistance (before and after exposure).
- Seam strength of factory and field-prepared seams (before
and after).
- Tear resistance (before and after, except fabric-reinforced
sheeting.
- Tensile properties (before and after exposure).
- Thickness (before and after exposure).
- Water vapor transmission (unexposed).
61
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The measurement of these properties represents a body of tests which can be
used to assess the effects on a liner of an environmental exposure. A
change in one property during an exposure is usually accompanied by changes
in other properties, but at this stage in liner testing no one property or
combination of properties has been correlated with liner performance in the
field. In the subsequent subsections, we discuss these properties and how
they are tested.
Prior to exposure to the wastes, all of the polymeric membranes were
subjected to the tests listed in Table 15. Results of these tests are
shown in Appendixes F and G. They served as reference points to measure
retention of properties on exposure. Because of the small size of the slab
specimens exposed to wastes, weather, etc, the tests performed after
exposure were modified and reduced in number of replicates. These tests
and the number of replicates are also listed in Table 15.
TABLE 15. TESTING OF POLYMERIC MEMBRANE LINERS
Test
Unexposed
sheeting
Exposed
sheeting
Analytical properties
Specific gravity, ASTM D297, D792
Volatiles, Appendix L
Ash, ASTM D297, Section 35
Extractables, Appendix M
Physical properties
Thickness
Tensile strength and elongation
at break*, ASTM D412
Hardness, ASTM D2240, 5 sec
Duro A and Duro D if Duro A >80
Tear strengthb, ASTM D624, Die C
Puncture resistance, FTMS 101B,
Method 2065
Yes
Yes
Yes
Yes
Yes
5 in each
direction
measurements
5 specimens
in each
direction
specimens
No
Yes
No
Yes
Yes
3 in each
direction
measurements
3 specimens
in each
di rection,
specimens
Seam strength, in peel and in shear,
ASTM D413
Water absorption or extraction at room
temperature and 70°C, ASTM D570
Water vapor permeability, ASTM E96
3 tests in
each mode
3 at each
temperature
3 specimens
2 tests i
each mode
No
No
n
Properties using special dumbbell.
^This test was used initially in testing fabric-reinforced sheeting,
as well as unreinforced sheeting, but was dropped in the test of the
fabric-reinforced sheeting.
62
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Analytical Properties of Polymeric Membrane Liners--
Because of the wide range of compositions and constructions of flexi-
ble polymeric membrane liners that were available at the time this project
was initiated and were developed during the course of the project, analysis
and fingerprinting of the membranes were needed. Analysis of a polymeric
membrane liner furnishes information to:
1. Characterize and identify the specific sheeting.
2. Use as a baseline for monitoring the effects of exposure on the
liner.
3. Assess the aggressive ingredients in the waste liquids that were
absorbed by the polymeric membrane liners to determine the com-
patibility of the liner with the waste liquid.
During exposure to waste liquids, polymeric liners may change in
composition in various ways that may affect their performance and result in
actual failures. Polymeric materials may absorb water, organic solvents
and chemicals, organometallic materials, and possibly some inorganics if
the liners become highly swollen. On the other hand, the extractable
components of the original liner compound may be leached out and result in
stiffening and even brittleness on the part of the liner membrane. The
solid constituents of a polymeric compound (which include carbon black,
inorganic fillers, and some of the curing agents) will be retained in the
liner compound, as will the polymer of which the liner is made (particu-
larly if the polymer is crosslinked). If organic materials are similar to
the liner in solubility and hydrogen bonding characteristics, the liner may
swell excessively. The volatiles and extractables were determined as part
of the testing procedure for measuring the effects of exposure.
The following subsections describe the analytical tests performed on
the polymeric membranes in this study.
AshThe ash content of a liner material is the inorganic fraction
that remains after a devolatilized sample is thoroughly burned at 550±25°C.
The ash consists of (1) the inorganic materials that have been used as
fillers and curatives in the polymeric coating compound, and (2) ash
residues in the polymer. Different liner manufacturers formulate their
compounds differently and determining the ash content can be a way to
"fingerprint" a polymeric liner compound.
The residue obtained by ashing can be retained for other analyses
(such as metals content) needed for further identification and for provid-
ing a reference point to determine trace metals that may have been absorbed
by the liner. The test method described in ASTM D297, "Fillers, Referee
Ash Method," Section 34, is generally followed in performing this analysis.
Ash contents of unexposed membrane liners were determined in accordance
with this method. The results for unexposed membranes are presented in
Appendix F.
63
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Exposed membranes were ashed in the early stages of the project to
assess the amount of inorganics that might have been absorbed. This
analysis was dropped because increases were very small when based upon the
polymer content of the compound.
Extractables--The extractables content of a polymeric sheeting is the
fraction of the compound that can be extracted from a devolatilized sample
of the liner with a solvent that neither decomposes nor dissolves the
polymer. Extractables consist of plasticizers, oils, or other solvent-
soluble constituents that impart or help maintain specific properties such
as flexibility and processibility. A measurement of extractables content
can be used as part of the fingerprinting of a sheeting. More recently the
extracts from liners have been analyzed (Haxo, 1983).
During exposure to a waste, the extractable constituents in a liner
may be removed, which may result in property changes. At the same time,
the liner may absorb nonvolatilizable constituents from the waste. Measur-
ing the extractable content of unexposed lining materials is therefore
useful for monitoring the effects of exposure. The extract and the ex-
tracted liner obtained by this procedure can be subjected to further
analytical testing, e.g. gas chromatography, infrared spectroscopy,
thermogravimetry, etc, for fingerprinting of the liner.
The procedure for extraction generally follows ASTM D3421, "Extraction
and Analysis of Plasticizer Mixtures from Vinyl Chloride Plastics," and
ASTM D297, "Rubber Products-Chemical Analysis," Paragraphs 16-18. Because
of the wide differences among the polymers used in liner manufacture,
a variety of extracting media must be used. The method followed in this
work is presented in Appendix M which indicates the media used for the
extraction of the membranes of each polymer type.
During exposure, the extractable content of the original materials can
increase or decrease depending upon the waste and the length of exposure
(Haxo, 1983). In performing an analysis for extractables, the volatiles
were removed first. Since some of the extractables may have been somewhat
volatile, care was taken to make sure that the volatile extractables were
not lost in the analysis. As indicated above, the extractables can be ana-
lyzed to determine the organic species that may have been absorbed during
exposure. These analyses, however, were not performed in this project.
Specific GravitySpecific gravity is an important property of a
membrane liner material which is comparatively easy to determine and can
give an indication of the composition and identification of a polymeric
compound. Specific gravity of exposed specimens can be measured only after
the specimen has been devolatilized. However, to make this determination,
care must be taken to thoroughly air-dry the specimen before placing it in
the oven at 105°C for final drying because dissolved or occluded moisture
can form steam and voids in the compound. ASTM Method D792, Method A, and
D297, Paragraph 15, are generally used in measuring specific gravity. In
this study, we found that specific gravity values of exposed materials were
erratic and not sufficiently informative; consequently, we discontinued
this test.
64
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VolatilesThe volatile fraction is represented by the weight lost by
an unexposed specimen of the liner on heating in a circulating air-oven at
105°C for two hours. Polymeric compositions generally contain a small
amount of volatiles (<1.0%), usually moisture. The specimen used in this
study was a disk cut from the membrane.
The test for volatiles was also used to determine the direction of the
grain that had been introduced in the membrane during manufacture. By
identifying the orientation of the 2-in. disk specimen with respect to the
sheeting at the time the specimen was died out, the grain direction can be
identified. The grain direction must be known so that tensile and tear
properties can be determined in machine (grain) and transverse directions.
Upon heating in the oven at 105°C, most sheetings with a grain will shrink
more in the grain direction than in the transverse direction.
Volatiles need to be removed before determining ash, extractables, and
specific gravity. Ash and extractables are reported on a dry basis (db).
Volatiles contents of the unexposed membrane liners are presented in Appen-
dix F. Monomeric plasticizers that are generally used in PVC compositions
have a limited volatility and can slowly volatilize at 105°C. Thus, the
air-oven test must be limited to two hours. The procedure used for the
determining the volatiles of the unexposed membranes is presented in
Appendix L.
After exposure to a waste, a membrane generally increases in volatile
content which, in most of our work, was made up primarily of water but also
can contain volatile organics. In this project, no attempt was made to
differentiate between these two volatiles. In our recent work, however,
the volatiles due to moisture and those due to organics are identified
(Haxo, 1983).
As performed in this project, the volatiles were removed by air-drying
the disk specimen at room temperature for a week, after which the tempe^a-
ture was raised to 50°C and held for 20 hours. The specimen was then
heated for two hours at 105°C. Most of the volatiles data on exposed
materials were obtained by this method.
Physical Properties of Polymeric Membrane Liners--
Tensile properties--Tensi1e properties of polymeric sheetings are mea-
sured in tension with a stress-strain tester. The properties that are mea-
sured depend on the type of polymeric sheeting and include the following:
- Tensile at fabric break (if fabric-reinforced).
- Elongation at fabric break (if fabric-reinforced).
- Tensile at yield (if semi crystal line).
- Elongation at yield (if semi crystal line).
- Tensile at break of sheeting.
- Elongation at break of sheeting.
- Stress at 100% and 200% elongations.
65
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Tensile testing is probably the most widely used test method in the
rubber and plastics industries for testing polymer compositions and pro-
ducts. It must be recognized that, even for a given polymeric material,
the values for the tensile properties vary with speed of test, i.e. the
rate of jaw separation, specimen size, direction of test with respect to
the "grain" in the sheeting, temperature, and humidity. "Grain" is
introduced in a sheeting during the processes of calendering or extrusion
in the manufacture of the sheeting.
Changes in tensile properties can be used to monitor the effects of
exposure on a lining material. In many rubber and plastics applications,
a 50% loss in tensile strength or in elongation, or a 50% increase or
decrease in modulus, indicates that the product has become unserviceable.
These criteria are probably not applicable to liners; nevertheless, major
changes in properties after a relatively short-term exposure indicate the
incompatibility of a liner and a waste.
At the time the project was initiated, we were interested in exploring
the effects of exposure on properties on an equal basis. It was decided
to test the tensile properties of all of the materials in accordance with
the same test method so that comparisons could be made directly without
having to make allowances for differences that would arise from the use of
different procedures. ASTM Method D412 was selected because of the shape
and size of the Type IV dumbbell and the applicability of the somewhat
smaller special dumbbell. The size of the dumbbell allowed for the re-
quired number of specimens needed to test the exposed lining material
samples in contrast to the ASTM D751 grab tensile specimen size required
for fabric-reinforced membranes. The shape of the dumbbell ensures that
failure will occur within a certain test area in contrast to strip speci-
mens pulled in accordance with ASTM D882, which tend to break in the jaws.
Thus, given the exploratory nature of our study, using a dumbbell-type test
specimen and a test speed of 20 inches-per-minute were the most appropriate
for determining changes in tensile properties during exposure.
In the later stages of the project, when crystalline sheetings came to
be of interest, limited testing was performed at 2 ipm because of the sen-
sitivity of these materials to speed of test.
Note: The test procedures followed currently in determining tensile
properties for the different types of sheetings are:
Thermoplastic polymers ASTM D882
ASTM D638
Cross!inked rubbers ASTM D412
Semi crystal line polymers ASTM D638
Fabric-reinforced sheetings ASTM D751, Methods A and B
Selvage edge of fabric-
reinforced sheeting ASTM D882, D638, or D412,
depending on the type of
polymer coating compound
66
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Modulus of elasticityThe nodulus of elasticity is a measure of the
stiffness or rigidity of stiff materials such as HOPE; it is defined as
the ratio of stress to corresponding strain in the part of the stress
strain curve that behaves according to Hooke's law, i.e. the stress values
are linear with respect to the strain. It is also known as Young's modu-
lus. ASTM D883, Method A, is followed in determining the modulus of
elasticity of semi crystal! i ne sheetings. This test was used only with
semi crystalline materials in the later stages of this project when HOPE and
polypropylene membranes became of interest. Data on modulus of elasticity
of the unexposed semi crystalline materials are reported in Appendix F.
HardnessHardness, in terms of the standard tests for hardness
of polymeric materials, is the ability of a material to resist indenta-
tion by a small probe of specified shape and dimensions. Although no
simple relationship exists between hardness as determined by indentation
and other measured properties, it is related to Young's modulus (ASTM
D1415-81). Hardness is an easily measured indicator of a quality of a
polymeric material and can be used to monitor change in a material. ASTM
D2240 is generally used to measure this property; the A scale is used
for soft, rubbery materials and the D scale is used for hard materials,
i.e. materials that are harder than 80 measured on the A scale. Both
instanteous- and 5-second readings are taken, but most of the hardness data
reported are 5-second readings.
Tear resistanceTear resistance is a measurement of the force re-
quired to tear a specimen with or without a controlled flaw. The measure-
ment serves as an indication of the quality of the compound and of the
mechanical strength of a sheeting, particularly to the type of stresses
often encountered during liner installation. The magnitude of the tear
resistance value is sensitive to the rate of test and the shape and size of
the test specimen.
As with the tensile testing, it was decided that all sheetings should
be tested in accordance with the same test method, which in this case was
ASTM D624 with Die C. It was recognized that this test method was in-
appropriate for testing fabric-reinforced sheetings. It was used in the
initial testing of all sheetings but was later dropped from the testing of
the fabric-reinforced liners. This subject is discussed further in Sec-
tions 6 and 7. All sheetings were tested with a crosshead speed of 20 i pm
until semi crystalline sheetings came to be of interest. Additional testing
of these later materials was then performed at 2 ipm.
Note: Coated fabrics are normally tested in accordance with ASTM
D751. Most fabric-reinforced membrane liners are a
special type of coated fabric because of the low thread
count of the fabric and the low adhesion of the coating to
the fabric. Because of the low adhesion between the
fabric and the polymer coating, when testing in strict
accordance with ASTM D751 the fabric pulls out of the
polymer matrix resulting in the threads bundling at the
tip of the tear and yielding excessively high test values.
67
-------
As a consequence, the liner industry currently uses a
larger test specimen to test tear resistance than that
called for in the ASTM method, i.e. 8 x 8 in. instead of
4 x 8 in.
Puncture resistancePuncture resistance is a measurement of the force
required to force a standard probe of a standard configuration through a
membrane at a given rate. The measurement serves to indicate the ability
of a material to withstand puncture from above, e.g. equipment, foot
traffic, deer hooves, etc and from below, e.g. by irregularities in the
substrate, etc. We have used puncture resistance to measure the effects of
an exposure on a sheeting; however, there is no universally accepted method
for measuring puncture resistance. Nevertheless, two Federal Test Method
Standards have found use in assessing puncture resistance of sheetings:
1. FTMS 101B, Method 2031, in which the force to slowly puncture a
sheeting by a tetrahedral probe is measured. The specimen is a
10 x 4 in. strip.
2. FTMS 101B, Method 2065, in which the force required to puncture a
sheeting with a tapered probe having an end of 0.25-in. diameter
is measured.
Because of the small size of the exposure test specimen, we used the method
described in Federal Test Method Standard 101B, Method 2065, for measuring
puncture resistance, particularly of unreinforced sheetings. The useful-
ness of this test for fabric-reinforced flexible membrane is limited
because of the openness of the weaves normally used. It does not measure
the resistance to puncture of a liner by a sharp object falling on the
sheeting during installation. However, considering the exploratory
nature of the project and since the size of the specimen required for the
puncture test with the tetrahedral point (FTMS 101B, Method 2031) was
too large in relation to the exposure sample, it was decided that the
fabric-reinforced materials would also be tested in accordance with FTMS
101B, Method 2065.
Water vapor transmissionTo measure water vapor transmission, ASTM
E96 Method BW was used. In this test, a cup with a membrane specimen cover
is placed in an inverted position in a controlled temperature, humidity,
and air stream. Loss in weight of water from the cup is observed as
a function of time. This test is intended for those applications in which
one side is wetted under conditions where the hydraulic head is relatively
unimportant and the moisture transfer is governed by water vapor diffusion
forces. The driving force is supplied by the difference in the relative
humidity on the two sides of the membrane. Moisture vapor transmission
results are reported in Section 9.
Water absorptionAbsorption of water can have adverse effects on many
polymeric compositions. Since most waste fluids contain water, the effects
of immersion in water on lining materials need to be determined. The
effects are monitored in terms of either change in weight, change in
dimensions, or both. A water absorption test is included to provide a
68
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relatively precise comparative index of all the sheetings in the test.
Extended immersion periods are recommended. The test specimens are large
enough to die out a tensile dumbbell or to pull as a strip to get an
indication of the effect of water absorption on tensile properties.
Water absorption tests at elevated temperatures accelerate the effects of
immersion in water. We performed water absorption tests on selected
sheetings at room temperature (23°C) and at 70°C in accordance with ASTM
D570 and the results are presented in Table 16. These and other results
indicated that water absorption tests run at 70°C were too severe to serve
as accelerated aging tests for most materials. We now use a temperature of
50°C for such testing.
Note: Resistance to environmental stress-cracking--This is a
property that was not used in this work but is of impor-
tance with semi crystal line polymeric materials and should
be considered in assessing them. Under certain conditions
of stress and exposure to soaps, oils, detergents, or
other surface-active agents, certain grades of plastics,
e.g. polyethylene, may fail by cracking at stress levels
below tensile strength. Proper selection of the poly-
ethylene or the addition of one of a variety of rubbery
polymers to the HOPE can eliminate this deficiency in
polyethylenes. ASTM D1693 can be run to indicate the
susceptibility of a polyethylene sheeting to environmental
stress-cracking. In this test, specimens having a control-
led imperfection are bent and exposed to designated
surface-active agents. Failure comes with breaking of the
specimen. A stress-crack is defined as an external or
thermal crack in a plastic caused by tensile stresses less
than its short-time mechanical strength.
Testing of Seam Strength of Factory and Field Systems--
A critical factor in the functioning and durability of a polymeric
membrane liner in service is the seam strength between assembled panels of
the sheeting. Testing of seams was performed to ensure that the method of
seaming a particular material is adequate.
Seams were tested in shear and peel modes. Elevated temperatures are
often used in seam strength tests. The peel test of seam strength is
significantly more sensitive to the effects of aging and exposure than is
shear testing.
Seam strength in shear was measured in accordance with ASTM D882,
Method A, modified so as to allow for the testing of 1-in. wide strips
containing a seam. The use of this method arises from ASTM D3083, the
PVC liner standard, which recommends that shear tests be performed in
accordance with ASTM D882, which is a strip tensile test. The National
Sanitation Foundation and others are using this method. Seam strength in
the peel mode was measured in accordance with ASTM D413, Machine Method
Type B, in 90° peel.
69
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TABLE 16. WATER ABSORPTION OF PRIMARY POLYMERIC MEMBRANE LINER MATERIALS AT ROOM TEMPERATURE AND AT 70°ca
Water
absorbed, % by
weight
At room temperature
Liner
Polymer number^
Sutyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
57R
77
6R
36
26
43R
75
59
1
week
0.82
1.63
3.44
0.39
1.20
3.80
1.07
1.59
11
weeks
3.22
5.53
6.97
0.52
1.84
13.62
1.05
2.34
44
weeks
4.50
10.2
10.9
0.0
1.49
37.8
0.67
2.43
100
weeks
6.4
12.5
16.3
4.5
2.56
75.1
1.31
2.98
159
weeks
10.92
16.85
20.81
0.93
3.85
67.20
1.61
4.53
186
weeks
10.76
16.51
19.42
0.38
3.61
63.11
0.36
1.55
1
week
4.62
15.9
22.1
0.36
1.44
14.1
1.28
4.87
11
weeks
17.54
58.4
131.0
0.45
4.52
107.0
1.10
8.25
At
44
weeks
53.9
140.0
245.6
0.57
11.20
240.0
0.72
24.0
70°C
100
weeks
103.2
179. ^
370.5
8.7
17.4
d
0.22
25. 5e
159
weeks
c
178.89
38.16
-4.19
21.08
d
0.79
26.176
186
weeks
141.3
196.14
471.40
-8.48
22.60
d
d
26.86e
aASTM D570-63 specimens (1x3 inches) in deionized water.
bR indicates that liner was fabric reinforced.
cSpecimens not weighed.
dSpecimens disintegrated.
eSpecimens became hard, indicating loss of plast-icizer.
-------
Fabrication and Mounting of Membrane Liner
Specimens in Cell?
Test specimens of the flexible membranes to place in the cells for
long-term exposure were fabricated as shown in Figure 8. Each test speci-
men featured a seam that could be tested both in shear and peel modes.
Each seam was made according to the instructions of the specific membrane
supplier and, in some cases, with his materials. The seams were 2-in. wide
and were parallel to the machine direction of the sheeting as is usually
encountered in the seaming of sheets. In the case of fabric-reinforced
membranes, the top piece, "B", incorporated in the seam a selvage edge
which faced the waste, thus avoiding exposing the cut ends of the reinforc-
ing fabric directly to the waste liquid. The underside of the liner has a
1.5-in. tab left free for peel testing.
20"
° 2.5"
0
O
.
e
'
t
5.25" _^
Pull Tab
2" SEAM
O
ID
CS
A
O O 0
-FLANGE
SELVAGE
AREA
B
O
0
O
O
c
0
1
O
,
2" SEAM
^
0 O
O
0
in *-
tN
0
15"
BOTTOM PIECE
11"
UPPER PIECES FACING WASTE
Upper
pieces
Bottom
piece
ISOMETRIC DRAWING
(Sketch not to scale)
Figure 8. Test specimens for long-term
primary cells. Pieces A and B
1.5-in. strip of polyethylene
peel tab. Piece C is butted
tacked in place as a spacer to
around the cell flange area.
exposure of membranes in
are seamed together with a
along the edge behind the
against the seam edge and
produce a double thickness
71
-------
Prior to fabricating the liner specimens to place in the long-term
exposure cells, sample seams were made and tested. If the seams were
satisfactory, fabrication of the specimens began. Seams were considered
satisfactory if, when tested in shear, they did not fail in the adhesive.
In the case of vulcanized liner materials, the seams of which intrinsically
fail in the adhesive, the seams were considered satisfactory when they
reached strength levels previously determined to be acceptable. If the
seams were unsatisfactory, a second set of sample seams was made and
tested. In some cases, cleaning of the liner surface prior to seaming had
been inadequate; in others, insufficient adhesive had been applied.
Figure 9 shows an unassembled exposure cell, with a membrane liner
specimen, prior to assembly (Haxo et al, 1977). Table 17 presents results
of the testing of seams in unexposed liner specimens.
Figure 9.
Unassembled exposure cell used for membrane liner specimen.
Shown are the tank and the base filled with silica gravel
and a membrane liner specimen (Haxo et al, 1977).
The polymeric membrane specimens, with the exception of neoprene, were
mounted in the cells with a sealing caulk applied to the upper surface of
the specimen facing the flange of the tank. A gasket of 0.25-in. closed-
cell neoprene sponge was placed between the liner specimen and the flange
of the base. The sponge gasket compensates for irregularities in the two
flanges and allows for a better seal. The neoprene liners were mounted
with the same 0.25-in. neoprene sponge on the upper side of the liner and
no caulk was used.
72
-------
TABLE 17. ORIGINAL STRENGTH QF SEAMS IN MEMBRANE LINER SPECIMENS MOUNTED IN PRIMARY CELLS
Polymeric membranes,
Item
Method of bonding
Width of lap seam, in.
Time after seaming, days
Peel strength (avg)c, ppi
Peel strength (max), ppi
Locus of failure1^
Shear strength6 (max), ppi
Locus of failure1^
% of tensile strength of
liner^
Test Butyl
method 57
Cement
LTVa
2
39
ASTM 1876 8.0
(Modified)
8.8
AD
ASTM D882 >84.8
CL
>119
CPE
77
Solvent
2
234
21.4
22.4
AD
48.3
SE
71
CSPE
6R
Cement
2
40
23.2
28.5
AD+DEL
62.1
SE
120
ELPO
36
Heat
0.5
b
21.0
SE
28.8
SE
49
Matrecon
EPDM
26
Cement
LTV*
2
293
4.9
5.2
AD
39
AD
54'
serial numbers
Neoprene
43R
Cement
LTV a
2
39
8.2
9.1
AD-LS
45.7
AD-LS
92
Polyester
el astomer
75
Heat
0.5
b
20.8
SE
>21.2
CL
>45
PVC
59
Sol vent
2
39
15.2
16.0
AD
>69.1
CL
>39
aLTV = Low temperature vulcanizing or curing.
^Seams made by supplier.
cStrip specimen 1-in. wide; initial distance between jaws, 2 in.; rate of separation of jaws, 2 ipm.
dLocus of failure:
CL = Break at clamp.
SE = Break at seam edge.
AD = Failure in adhesive.
AD-LS = Failure between adhesive and liner surface.
DEL = Del ami nation in liner.
eStrip specimen 1-in. wide; initial distance between jaws, 4 in.; rate of separation of jaws, 2 ipm.
f
Shear value measured at 2 ipm
Force to break liner (from tensile strength test at 20 ipm)
x 100.
-------
Two caulking compounds were used in sealing the liners. Since the
caulks were exposed to the waste, they were chosen on the basis of pre-
liminary screening tests (Section 6). We used a butyl caulk with the acid
and caustic wastes and a polysulfide caulk with the other wastes.
After allowing time for the caulk to cure, the cells were tested by
filling with water. A couple of the cells leaked slightly, but could be
sealed by tightening bolts in the cell flanges to compensate for the
compression set taken by the neoprene foam. One liner had to be completely
remounted. Another cell that passed the water test and was filled with
waste developed a slight seepage between the liner and the exposure cell
tank. This liner eventually had to be remounted.
74
-------
SECTION 6
EXPOSURE IN PRIMARY CELLS
INTRODUCTION
The principal effort of this project was to assess experimentally
a range of lining materials under conditions that simulate the service
of liners in place in waste storage and impoundment facilities. The
objectives of this part of the project were to expose a sufficiently large
sample of each selected liner material to different wastes, to measure
the effects of the exposures upon properties, and to measure the quantity
and quality of the waste that passes through the liner, particularly in the
case of soils and admixes. The results were to be used to assess the
general performance of the selected lining materials in contact with actual
wastes and to determine their durability. Ultimately, it is desired to
be able to estimate service lives of lining materials under different
conditions.
In this section the design and construction of the test cells in which
specimens of the lining materials were exposed are described as are the
preliminary compatibility test procedures which led to the selection of
combinations of waste streams and lining materials for the long-term ex-
posure testing. The monitoring of the test cells during exposure is des-
cribed with particular emphasis on the soil and admixed lining materials.
The recovery of the liner materials after usually two exposure periods is
described and unusual effects are noted. Finally, for each of the liner
types, the results of exposure are presented and discussed. A complete
tabulation of the exposures of the liner specimens in the different wastes
is presented in Appendix A.
DESIGN AND CONSTRUCTION OF PRIMARY EXPOSURE CELLS
AND ANCILLARY EQUIPMENT
Primary Exposure Cells
Each individual exposure cell was designed to perform as a permeameter
and to be adaptable to liner specimens ranging from 20 mils to 12 in. in
thickness as shown schematically in Figure ]0, for membranes and thick
liner specimens. The cell provides for test specimens 10 x 15 in. in area
and a volume of waste of approximately 1 cu ft at a depth of 1 ft. Photo-
graphs of the exposure cells for thick admix specimens and for membrane
liners are shown in Figures 9 and 11.
75
-------
Top Covir
Epoiy
Sttil Tonk
Outltt tubt with
Epony-coottd
Diaphrogm
-Top Covtr
Epoxy
Cootid-
BoH
Flonged Steel
Spocer
W 0 I t »
^Nioprent Spongt Goiktt
~Epoxy Grout Ring
ADMIX LINER
£poxy and Sand
E^ Cooling
^^^""^f"^^ " " "* *
Wottt Column:
10'il5"«l2"High
Outlit tubt with
Eposy-cootid
Diaphragm
«1 .- I* 'I> *' " ' f ""-
** ".i Cru»h«d Sillco
Figure 10. Design of cells for long-term exposure of membrane liners
(top) and soil and admix liners (bottom) to the different
hazardous wastes. A liner specimen is 10 x 15 in. in area.
76
-------
Figure 11. Unassembled exposure cell used for thick admix specimens.
Shown are the three components, the tank, the spacer for the
thick liners, and the base loaded with silica gravel. Shown
also is an hydraulic asphalt concrete specimen.
One hundred forty-four cells were fabricated from 11-gauge steel,
coated on the inside with a chemically resistant epoxy coating, Epoxy 3,
and on the outside with a rust-preventive paint. (See Appendix H for
details regarding materials used in constructing cells and mounting liner
specimens.)
After the first 24 cells were coated with paint brush and pad, it was
decided that spraying would be a more economical way to coat the remaining
120 cells. A jig was constructed to facilitate the coating of the cell
tank interiors. The cell bases were laid out next to each other on long
tables so that 20 could be sprayed as a group.
The spraying of the primer presented no problem as its viscosity was
within the medium range for paint. Spraying of the two-part epoxy coating,
Epoxy 2, was somewhat more difficult; a quart of the mixed coating has a
potlife of 42 minutes at 77°F and a viscosity of 30 poise, the consistency
of a very heavy paint.
One coat of the primer was applied, followed by a coat of the two-part
epoxy coating, Epoxy 2. A second coat of Epoxy 2 was applied along the
bottom weld on the tank sections. All coatings were tested for pinholes
with a spark tester.
77
-------
The bases of the cells were finished similarly to the tanks. They
were filled with a chemically-inert high quality crushed silica in order to
prevent reactions and contamination of the waste which might seep through
the liner.
Spacers for mounting the admix liners were fabricated of different
heights, depending on the thickness of the liner. For those liners com-
pacted in-place, i.e. the soil-cement, native soil, and the modified
bentonite, the inside surfaces were coated first with the primer and Epoxy
2, and then with a second coat of Epoxy 2 sprinkled with sandblasting sand.
The rough wall surface was formed to reduce or eliminate a wall effect
which might result in the waste by-passing the liner. A ring seal of
epoxy-sand was cast around the periphery of soil, the admix, and the
sprayed-on liner specimens to increase path length of the waste percolating
through the liner and to reduce further the possibility of wall effects and
channeling. The rings were cast of Epoxy 1 and Epoxy 2 filled with sand-
blasting sand (Appendix H).
Lids for each of the 144 cells were fabricated of hardboard, wood, and
polyethylene, and installed on the filled cells. These lids reduced water
loss by evaporation and prevented accidental contact with the hazardous
waste by people or animals; they were not intended to be either water or
air-tight.
Rack for Holding Exposure Cells
The exposure cells were mounted on a rack constructed outdoors on a
concrete slab at the Richmond Field Station of the University of Cali-
fornia, Berkeley. This rack consisted of 6 sections, each of which held 24
exposure cells. Each section had 2 tiers and was 4 x 8 x 3 ft. These 6
sections were arranged in 2 rows of 3 sections each, which were placed 4 ft
apart, as shown in Figures 12 and 13. A corrugated plastic cover was
constructed over the rack at a height of 8 ft to protect the cells from
rain and sunlight. The design of the racks afforded good access to the
cells; each could be removed or replaced with relative ease.
Although the cells were outdoors, they were well protected from the
heat of the sun. The temperature was relatively uniform, generally in the
range of 50 to 60°F, and did not drop below freezing.
Silica Gravel
The gravel used to fill the cell bases and support the liners was a
crushed quartz from the Bear River (California); it was selected because of
its high silica content (99%) and the low content of constituents soluble
in acid which might contaminate the seepage through the liner specimens.
The seepage was to be collected and characterized to assess the attenuation
by and time for waste to percolate through the liner. The nominal size was
3 to 6 mm (0.125 to 0.25 in.); individual pieces of stone were as long as
25 mm in one dimension, since the gravel had been crushed in a jaw crusher
which tends to produce a high percentage of long and flat particles. The
gravel was thoroughly washed and dried before placing in the bases.
78
-------
Figure 12. Overall view of the rack holding the exposure cells,
Figure 13. View of cells on the rack. These include cells contain-
ing membrane and admix liners.
79
-------
SOILS
Selection of Wastes for Exposure to Soil Liner
A preliminary series of tests of the compatibility of the Mare Island
soil was run with the different wastes that had been obtained. The objec-
tive of this testing was to determine which wastes should be placed in the
long term exposure test as it was desired to include only those combina-
tions of liners and wastes that would not fail in a short time. The lead,
oily, and pesticide wastes were considered compatible with the soil and,
therefore, were not included in the compatibility test.
The compatibility test that was used for the soil is described by Haxo
et al, 1977. Basically, it consisted of sealing 2-in. diameter cylindrical
specimens in one end of 8-in. long, 54-mm i.d. Pyrex cylinders with Epoxy 1
and Epoxy 4 (Appendix H). Three days after the epoxy cement was cast, the
cylinders were filled with the wastes to a depth of 5 inches.
The fine-grain soil specimens were prepared by molding the soil at a
water content of 20 parts per 100 parts dry soil in a 2-in. diameter mold.
The soil was compacted in 5 lifts with a high-frequency impact tool fol-
lowed by double-end static compaction. The height of the specimens was
about 2 inches.
The specimen in acidic waste, "HN03-HF-HOAc", released a few bubbles
immediately and continued to release bubbles slowly for about a week.
Within one day the surface of the specimen developed a flaky appearance and
the epoxy peeled off the glass in both "HN03-HF-HOAc" and "Spent caustic";
within 2 days the same effect was noted with the specimen in "Slop water."
When probed with a glass rod after 7 days of exposure, the specimen
exposed to "Slop water" had a hard surface; the specimen exposed to "Spent
caustic" was soft on the surface, and the surface of the specimen exposed
to "HN03-HF-HOAc" was flaky. There was no leakage from any of the speci-
mens. After 11 days of exposure, a slightly damp spot appeared at the
center of the bottom of the specimen exposed to "Spent caustic." After 16
days the damp spot remained unchanged and was neutral to litmus paper.
Because of the bubbling and the flaky appearance of the soil, it was
decided to delete the acid waste "HN03-HF-HOAc" from the primary exposure
test. The wastes included in the primary exposure test of the soil liner
and the number of cells into which each was loaded are shown in Table 18.
Monitoring the Cells
The monitoring of the cells consisted of:
1. Measuring the amount of liquid seeping through the liner. Data
were kept for incremental collections as well as cumulative
collections as a function of time.
80
-------
2.
3.
Measuring the level of the wastes in the tanks periodically for
comparison with the seepage.
Determining the quality of the seepage effluent to assess the flow
of waste through the liner. The measurements included pH, elec-
trical conductivity, total solids, and, periodically, elemental
analysis.
TABLE 18. WASTES INCLUDED IN PRIMARY EXPOSURE
TESTS OF THE SOIL LINER
Identi f i
Type
Alkaline
Lead
Oily
Pesticide
cation of waste
Name
"Spent caustic"
"Oil Pond 104"
"Slurry oil"
"Weed killer"
Matrecon
serial
number
W-2
W-14
W-5
W-15
W-ll
Number
of
cells
2
2
2
2
2
A polybutylene bag was attached to the base of each of the cells
containing soil liners into which the seepage could continuously drain
freely. The polybutylene was an effective bag for this purpose as it
formed a durable seam. However, these bags had to he protected from the
light as the polybutylene was unpigmented. There were some losses of
effluent due to failure of bags because of UV degradation. The failed
bags were replaced with bags made of black polybutylene when it became
avail able.
The measurement of the composition of the effluent was important so
that changes in the waste that percolated through the liner would be
observed. Typical test results of the seepage are presented in Tables 19
and 20 and Figure 14 for two cells with soil liners and "Spent caustic"
and pesticide wastes. The results on these two cells are discussed below
in the subsection "Discussion of Soil Liner Results."
Dismantling of Cells and Testing of Soil Specimens
Four cells with soil liners were dismantled for testing the soils,
particularly with reference to the metals distribution in the soil follow-
ing exposure to the different wastes. The three cells containing "Spent
caustic" waste, lead waste, and "Oil Pond 104" waste had been in exposure
for 958 days, and a cell containing "Slurry oil" waste had been in exposure
for 696 days. The wastes were removed from the tanks and then the spacers
with the soil liners were removed from the cell assembly.
The soil was sampled either by cutting narrow slits in the soil and
removing blocks of the liner material or by forcing a brass tube into the
liner, avoiding compaction, and noting original depths and locations. The
81
-------
TABLE 19. MONITORING OF CELLS - COLLECTION AND ANALYSIS OF SEEPAGE FROM CELL
WITH MARE ISLAND SOIL LINER AND SPENT CAUSTIC WASTE (W-2)
oo
ro
Date
3-5-76
4-3-76
11-15-76
2-1-77
6-23-77
11-19-77
5-10-78
9-15-78
4-27-79
2-4-80
4-21-80
9-15-80
11-7-80
2-6-81
5-7-81
8-7-81
11-6-81
2-8-82
5-7-82
8-6-82
11-10-82
2-8-83
5-6-83
Time,
Incremental
0
223
78
142
149
172
128
224
779
147
53
91
90
92
91
94
88
91
96
90
87
days
Elapsed
...
0
223
301
443
592
764
892
1116
1476
1623
1676
1767
1857
1949
2040
2134
2222
2313
2409
2499
2586
Amount, mL
Incremental
Cumul ati ve
Total
d i s s o 1 v e
sol ids,
d
pH
Waste level be-
low tank top, in.
... C r\ 1 1 a cc nmK 1 oH
282
472
860
500
635
480
724
fnl
253
17C
206
208
303
285
248
180
240
260
195
255
197
282
754
1614
2114
2749
3229
3953
lection lost
4206b
4223b
4429b
4637b
494flb
5225b
5473b
5653b
5893b
6153h
6348b
6603b
680Qb
\_« V- 1 1 U _» J V_MIl/ 1
Pol 1 f i 1 Inri
21.13
20.01
21.87
23.24
23.13
- bag repl aced
...
20.43
19.83
22.00
20.95
21.60
...
7.2
7.0
6.2
7.2
6.0
*
6.4
4.6
3.2
6.9
7.1
6.5
6.7
6.5
6.7
6.8
6.7
6.0
6.6
6.5
...
...
...
2.1
2.4
2.6
3.1
4.1
8.0
7.9
5.4
6.5
6.8
6.7
7.1
7.3
7.6
7.7
8.0
aData for April 21, 1980, represents 77 days accumulated seepage. A ruptured bag prevented accumu-
lation of seepage between April 27, 1979, and February 4, 1980.
bCumulative amount based on all available data but does not include estimates of lost collections
between April 23, 1979, and September 15, 1980.
cMost of collection lost.
-------
TABLE 20. MONITORING OF CELLS - COLLECTION AND ANALYSIS OF SEEPAGE FROM CELL
WITH MARE ISLAND SOIL LINER AND WASTE PESTICIDE (W-ll)
00
CO
Date
2-23-76
3-1-76
11-15-76
2-1-77
6-23-77
11-19-77
5-10-78
9-15-78
4-23-79
2-4-80
4-21-80
9-15-80
11-7-80
2-6-81
5-7-81
8-7-81
11-6-81
2-8-82
5-7-82
8-6-82
11-10-82
2-8-83
5-6-83
Time,
Incrementa
days
1 Elapsed
Amount
Incremental
, mL
Cumulative
Total
dissolve
solids,
d
pH
Waste level be-
low tank top, in.
4 ... . ,.., Poll a cc rtmK "I n/H
o
259
78
142
149
172
128
220
77a
147
53
91
90
92
91
94
88
91
96
90
87
0
259
337
479
628
800
929
1148
1512
1659
1712
1803
1893
1985
2076
2170
2258
2349
2445
2535
2622
r~n fn T^A
316
292
680
665
710
500
1035
Tnllr
22
2QC
193
295
325
283
320
251
315
330
266
166
207
316
608
1288
1953
2663
3163
4198
ction lost
4220b
4240h
4443b
4728b
5053b
5336b
5656b
5907b
6222b
6552b
6818b
6984b
719lb
19.48
19.01
18.13
16.75
15.42
13.56
- bag replaced
9.59
9.22
9.00
8.92
8.89
8.72
...
7.0
7.2
6.8
7.4
6.6
7.4
7.5
3.5
5.6
7.4
6.7
7.1
6.8
7.0
7.2
7.3
6.9
7.5
7.5
4.8
5.0
5.8
6.6
8.1
4.3
3.8
9.3
9.6
10.0
10.1
10.4
10.7
11.1
11.4
11.7
aData for April 21, 1980, represents 77 days accumulated seepage. A ruptured bag prevented accumu-
lation of seepage between April 23, 1979, and February 4, 1980.
bcumulative amount based on all available data but does not include estimates of lost collections
between April 23, 1979, and September 15, 1980.
cMost of collection lost.
-------
25
TOTAL DISSOLVED SOLIDS
MARE ISLAND SOIL/
PESTICIDE
CUMULATIVE SEEPAGE
1978 1979
TOTAL DISSOLVED SOLIDS
MARE ISLAND SOIL/
SPENT CAUSTIC
CUMULATIVE SEEPAGE
1976 1977 1978 1979
1980 1981 1982 1983
Figure 14. Monitoring of cells with Mare Island soil liner. The cumula-
tive seepage and the total dissolved solids of the seepage are
shown for the cell containing pesticide waste, which has a
total dissolved solids content of about 0.4%, and for the cell
containing the "Spent caustic" waste, which has a total dis-
solved solids content of approximately 22%. Adjustments were
made for the losses of seepage during the period between April
23, 1979 and September 15, 1980.
84
-------
samples, along with samples of exposed bentonite-sand mixtures and soil
cement, were then submitted to H.E. Doner of the University of California,
Berkeley for analysis of selected trace metals and study of metal migration
in the soi1.
Movement of Waste Constituents in the Soil Liners
Soil samples were analyzed for six chemical species by H.E. Doner.
The blocks or corings of soil were trimmed to remove possible contamination
on the surface. Samples were then taken by cutting sections at various
depths of the cores. The sampled sections were air-dried, ground, and
sieved through a 2 mm stainless steel screen and a subsample taken to
determine moisture content. Extraction of Cd, Cr, Cu, Ni, and Pb was
accomplished by digestion of 5.0 g soil in 30 mL 4N HN03 at 70°C for 16
hours (Ganje and Page, 1974) followed by the determination using a flame
atomic absorption spectrophotometer equipped with a background corrector.
Mercury was extracted from a sample 0.1 g by a mixture of KMn04, aqua
regia, and ^2^2^8 anc' analyzed by a mercury vaporization method with an
atomic absorption spectrophotometer. The analytical data for six chemical
species in three exposures ("Spent caustic," lead waste, and "Slurry oil")
are presented in Table 21. The last line of the table shows the background
concentration present in the unexposed soil. The distribution of cadmium,
chromium, copper, lead, mercury, and nickel in the soil liner after pro-
longed exposure to "Oil Pond 104" waste is shown in Figure 15.
TABLE 21. ELEMENTAL ANALYSIS AVERAGED OVER ALL
DEPTHS FOR MARE ISLAND SOIL
Metal concentration, yg/g oven-dried soil
Treatment Cadmium Chromium Copper Mercury Nickel Lead
"Spent caustic"
Lead waste
"Slurry oil"
Unexposed soil
0.37
0.43
0.39
0.29
61.9 .
60.6
59.9
60.8
65.4
70.7
70.3
65.0
0.34
0.31
0.37
0.32
79.9
89.8
89.3
88.9
30.2
a
30.9
28.1
aSee Figure 16.
The fact that the distribution of different chemical species on the
profile was uniform, and that the average concentration values for each of
the liners are close to the values for the unexposed soil, is a reflection
of the low concentration of the chemical species in the respective wastes.
This is shown to be the case for the "Spent caustic" and lead wastes in
Table 22. Table 22 also indicates that, unlike the lead and the "Spent
caustic" wastes, the "Oil Pond 104" waste is quite concentrated with regard
to the investigated chemical species. As a consequence, during the 31.5
months over which the flow was monitored, a clear profile was obtained
for all elements as shown in Figure 15. The concentrations of lead and
85
-------
p-g/g
250
500
4OO 0 I 2345
Figure 15. Distribution of cadmium, chromium, copper, lead, mercury, and
nickel in soil liner after 31.5 months (958 days) exposure to
"Oil Pond 104" waste.
86
-------
TABLE 22. CONCENTRATION OF SIX CHEMICAL SPECIES IN THREE WASTES3
Chemical
species
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Lead
u9 mL-1
0.76
1.9
1.1
95.0
0.06
0.90
1.4
3.5
9.2
6.0
3.1
N
x
...
x
X
X
X
ID'5
i
io-5
10-4
10-7
io-5
"Spent
\ig mL-1
0.6
0.8
2.3
5.0
0.003
1.8
Waste
caustic"
N
1.1 x
...
7.2 x
4.8 x
3.0 x
6.1 x
io-5
i
10~5
io-5
10-8
io-5
"Oil Pond 104
ug m
8
290
33
170
1
4
l_-l
.0
.0
.0
.0
.6
.0
N
1.4 x
*
1.0 x
1.6 x
1.6 x
1.4 x
II
10-4
ID"3
ID'3
10~5
10-4
aSee Table 3 for more details.
chromium are high in the "Oil Pond 104" waste; thus, these elements could
compete with major cations for adsorptive sites. The enrichment of lead in
the very top layer of the soil exposed to lead waste is shown in Figure 16.
e
o
ex
O)
Q
20
30
pig/g
50
100
Pb
N.S.,28n-g/g
Figure 16. Distribution of lead in soil liner after 31.5
months (958 days) of exposure to lead waste.
87
-------
Discussion of Soil Liner Results
Analysis indicated that the lead waste was a solution of 10~3 N
concentration with respect to lead, and this concentration was the main
reason for the sharp profile that is shown in Figure 16. This figure
indicates that, on the average, the concentration of lead in the contami-
nated soil was 80 yg g-1 at 0-2 cm and 44 yg g-1 at 2-5 cm. Taking into
account the lead concentration of 28 yg g~l in the unexposed soil, one
finds a concentration difference of 52 yg g~l for the first two centi-
meters and 16 yg g-1 for the next three centimeters of liner. Assuming
that all lead is divalent, these values correspond to 0.05 and 0.015 meq/
100 g soil, which is a level of adsorption below the equilibrium capacity
of a solution of 1.6 x 10~3 N concentration. Thus, one can say that when
the Mare Island soil was exposed to a waste with a high concentration of
lead, it retained lead and consequently exposed the underlying soil layer
to a smaller concentration of lead.
Figure 15 shows, in the case of "Oil Pond 104" waste, a retention of
all six chemical species in the first two centimeters of the soil liners.
Figure 15 also shows that, with the possible exception of copper, the
contamination with the five heavy metals was superficially localized,
i.e in the top two centimeters of the soil.
Analytical data concerning the concentration of the six chemical
species in "Oil Pond 104" waste (Column 2) is presented in Table 23.
TABLE 23. CONTAMINATION OF MARE ISLAND SOIL WITH SELECTED
CHEMICAL SPECIES WHEN EXPOSED TO "OIL POND 104" WASTE
Chemical
species
(1)
Cadmium
Chromium
Copper
Nickel
Lead
Mercury
Co
yg mL"1
(2)
8
290
33
4
170
1.6
aC0 = Concentrati
t>AC = Concentrati
a
0
(mN) 1
(3)
.142
11.15
1
0
1
0
on
on
.039
.136
.641
.016
ACb
[yg g-1)
(4)
14
380
250
70
300
3.1
(yg)
(5)
3.1
113.7
12.9
1.6
66.6
0.6
in "Oil Pond 104" waste.
difference between contami
c
(yg g"-'-)
(6)
10.9
266.3
237.1
68.4
233.4
2.5
nated and
ad
(meq/100 g)
(7)
0.0194
1.0242
0.7463
0.2330
0.2253
0.0025
uncon-
taminated soil.
= Mass of element present in one pore volume (1 PV) associ-
ated with 1 g of soil (1 PV = 0.392 mL), assuming elemental
concentration of liquid in pore space is equal to C0.
= Concentration of species either as precipitated constitu-
ent or as adsorbed cation.
88
-------
Column 3 of Table 23 is calculated assuming that all species are of
valence "+2"; this is not true for the chromium. Column 4 is the differ-
ence between the "exposed to Oil Pond 104" and unexposed soil and, there-
fore, is a measure of contamination. Column 5 is the amount of contaminant
corresponding to one gram of saturated soil (porosity equal to 0.509),
assuming that the concentration of a particular species in the pore liquid
is equal to its concentration in "Oil Pond 104" waste. Columns 6 and 7
represent the content of a species associated with the soil solid phase,
either as a precipitated constituent or more likely as an adsorbed cation.
Data in Column 3 indicate that the concentrations of cadmium, copper,
nickel, and lead vary between 1.36 x 10-4 N and 1.64 x 10-3 nt which is a
range characteristic for major constituents, such as Ca2+, in uncontami-
nated soils. Thus, one can expect this group of "trace" elements to
compete with cations, such as Ca2+, Mg2+, and K+, for adsorptive sites.
Since the cation exchange capacity of Mare Island soil is in excess of 10
meq/100 g soil and since the total milliequivalents (less chromium) in
Column 7 is exactly equal to 1 meq, the adsorptive potential of the 0-2 cm
layer has not been reached after 2.6 years of exposure.
The abrupt change in concentration at a very shallow depth for all six
elements with the "Oil Pond 104" waste, can be explained in several ways.
First, the concentration of chemical species in this waste is much higher
than in either the lead waste or the spent caustic; thus, the chemical
species were able to compete for adsorptive sites successfully. Second,
the low flow rate of 10"^ cm s~l resulted in a large residence time;
thus, cations and soil surfaces were provided sufficient time to interact.
Third, "Oil Pond 104" waste, being lighter than water and having low
solubility in water, should have yielded a quite abrupt oil-wetting front
with a minimal dispersion above and below the front.
Table 23 allows the calculation of the volume of "Oil Pond 104" waste
which must have percolated through the 0-2 cm layer to generate the reten-
tion indicated in Column 6, assuming that the cation-soil reaction is
far from the equilibrium and thus that all the cations in the liquid phase
are transferred into the soil matrix. Based on such an assumption, one can
calculate for the element cadmium, for instance, that 10.9 yg were adsorbed
as a result of the leaching of a gram of soil by 10.9/3.1, i.e. 3.52 PV of
"Oil Pond 104" waste. Adding to this value the 1 PV which is in the pore
space one obtains 4.52 PV. Since 1 PV corresponding to 1 g soil is equal
to 0.392 ml and there are 2348.4 g soil in the first 2 cm of the liner, the
total "Oil Pond 104" waste which must have reached the 2 cm depth is equal
to 4.16 L. Table 24 presents similar data for the other chemical species,
except chromium. The values for cadmium, lead, and mercury are well in the
range of the amount of "Oil Pond 104" waste which penetrated the surface of
the soil. The values for copper and nickel are several times as large as
the actual amount of leachate collected. This apparent anomaly can be
explained if one considers that at any time during the flow process the
soil surface is an "open" boundary between the oil which is already inside
the soil pore space and the oil above the liner; thus there is permanent
diffusion of cations from the "source" above ground into the "sink" inside
the soil.
89
-------
TABLE 24. VOLUME OF "OIL POND 104" WASTE
REQUIRED TO PERCOLATE THROUGH THE 0-2 CM
SOIL LINER TO PRODUCE THE CONTAMINATION
INDICATED IN TABLE 23a
Volume of "Oil Pond 104"
Element waste required, L
Cadmium
Copper
Nickel
Lead
Mercury
4.16
17.84
40.30
4.15
4.76
aln Column 4 of table.
In addition to the chemical considerations presented above, the cells
were monitored over a period of 6.5 years for flow rates and general
characteristics of the effluent, such as pH, electrical conductivity (EC),
and total dissolved solids (TDS). Figure 14 presents the cumulative
amounts of effluents and the concentrations of dissolved constituents (TDS)
for two representative cells; one cell contained a soil liner and was
loaded with pesticide waste and the second cell contained a soil liner and
was loaded with spent caustic. Similar graphs were constructed for all
cells, the flow behavior of which is analyzed in subsequent paragraphs.
This analysis is based on the following:
- Area of the flow boundary between the waste and the soil equal to
903 cm2.
- Soil volume in the cell equal to 27.53 L.
- Soil bulk density, p^ equal to 1.3 g cm~3.
- Soil mass in the cell equal to 35.8 kg.
- Soil porosity, n equal to 0.509.
- Soil effective porosity, n0 equal to 0.458 (as n0 assumed to be
0.9 n).
- Waste depth over the soil equal to 30.5 cm.
The results, calculated on the basis of these data and also on the basis of
an average TDS for each cell and cumulative infiltration (assumed equal to
total effluent) are presented in Table 25.
90
-------
TABLE 25. AMOUNT OF SALT DISCHARGED IN THE EFFLUENT AND AVERAGE
PERMEABILITY VALUES FOR COMPACTED SOIL LINERS
Waste
identification3
Pesticide (W-ll)
Pesticide (W-ll)
Lead waste (W-14)
"Oil Pond 104" (W-5)
"Spent caustic" (W-2)
Salt dis-
charged in
the effluent,
percent,
on soil
3.6
3.3
3.8
3.1
4.9
Effluent,
pore
volumes
0.79
0.67
0.91
0.60
0.63
Elasped
time*5,
days
2622
2622
2620
2611
2586
Average
ability
10-8 cm
2.7
2.3
3.1
2.0
2.2
perme-
00,
S-l
aMatrecon waste serial number in parentheses.
bAs of May 6, 1983.
The large TDS concentration in the effluents is the result of the
large proportion of salts in the original Mare Island soil. Figure 15
shows that, when the waste is pesticide and practically free of dissolved
salts, the TDS drops during the tested period to approximately half its
original value. This is to be expected if one considers that approximately
0.67 pore volume was leached. At the same time, salt in the Mare Island
soil diffused into the pesticide waste to increase the concentration of
salt. The original waste had a total solids value of 1.2% and an elec-
trical conductivity of 3,000 pmho. Late in the exposure the supernatant
waste had a total solids value of 3.1% and an electrical conductivity of
45,000 ymho.
In the case of the "Spent caustic" waste concentrated in TDS, this
fact is reflected by the high concentration of salts in the effluent
throughout the whole testing period of 6.5 years.
Table 25 indicates the low permeability of the Mare Island soil.
Because less than one pore volume of effluent was collected, the results
cannot be interpreted as reflecting the interaction between the Mare Island
soil and different wastes, but rather the permeability with regard to the
initial soil solution present in the freshly compacted soil. The charts
comprising flow data for all cells are very much alike both in terms of the
cumulative outflow values and in terms of the constancy of the K value
during the testing period for any one of the cells. Both features point to
the fact that Mare Island soil is quite insensitive to chemical treatment;
however, since only a small amount of waste crossed the waste-soil boundary
during the test period, this statement is made with caution. The fact that
the soil resisted alterations in flow properties, either as a result of
a change in the state of flocculation or because of volume changes or
matrix dissolution, is probably related to the very large ratio of none!ay
minerals:clay minerals in the fraction of soil smaller than 2 urn. Overall,
91
-------
the Mare Island soil performed quite satisfactorily during the first 6.5
years of exposure to a variety of hazardous wastes.
ADMIXED MATERIALS
Three types of admixed materials were included in this study, i.e.
asphalt concrete of hydraulic-grade, bentonite which had been treated with
a polymer, and soil-cement. The preparation of these materials is des-
cribed in Section 5. In this subsection, the compatibility testing and the
selection of wastes for the long-term exposure are described, and the
results of the testing over periods of up to 6 years are presented.
Asphalt Concrete
Selection of Combinations of Wastes and Liners--
Ten asphalt concrete liner specimens were selected for the exposure
test from those cut fron the sheet that was originally compacted on a
concrete slab. The selection was made on the basis of appearance and
uniformity of thickness, i.e. 2.5 in. Because of the sensitivity of the
asphalt to hydrocarbons, the oily wastes were not included in the exposure
test program of the asphalt concrete liners. The wastes and the number of
cells into which they were loaded are:
Acidic waste - "HN03-HF-HOAc" 2
Alkaline waste - "Spent caustic" 2
Lead waste - 2
Pesticide - "Weed killer" 2
Water - EBMUDa tap water 2
aEast Bay Municipal Utility District,
California.
The lead waste was included because it appeared to have been almost com-
pletely water; however, one component of the blend which made up the
lead waste used in the exposure tests did contain a significant amount of
hydrocarbon.
Monitoring of Cells--
After the cells were loaded with wastes, some leakage occurred mostly
through the seals around the edges of the tanks, but the waste did not seep
through the liner. Tightening the bolts around the flange was sufficient
in most instances to eliminate further leakage of this type, although it
was necessary to remount several of the cells.
Relatively early, seepage occurred through several of the asphalt
concrete liners, one from a cell containing a "Spent caustic" waste, one
from a cell containing lead waste, and the other two from cells containing
the strong acidic waste. It was necessary to remove these cells from the
92
-------
exposure test and dismantle them. In all cases, there were significant
leaks through the liners as determined by flooding the liners with water
and pressurizing the lower part of the cells and observing the bubbling of
air through the asphaltic concrete.
The asphalt concrete liner specimen taken from the cell containing
the acidic waste showed a considerable amount of dissolved aggregate at the
surface. Presumably, the effect on the aggregate was the result of reac-
tion of the aggregate with the waste which contained some hydrofluoric
acid; also, the top layer of the asphalt was quite spongy. This liner
specimen was cored to determine its properties and the properties of the
asphalt.
An asphaltic liner that had been in the cell containing the "Spent
caustic" waste showed leaks; they were all on one-half of the liner as
observed by pressurizing the base. We coated the top layer of the liner
in the area of the leaks with a seal-coat and returned the cell to the
exposure test, this time filling it with the second alkaline waste, "Slop
water," which was considerably more alkaline than the first. Only a
small amount of leakage occurred in the subsequent six years. No seepage
occurred in the liner in the second cell containing the "Spent caustic"
waste.
Of the cells still in operation in July, 1983, there has been no
seepage in either the second cell containing the lead waste or the re-
maining cell containing pesticide waste. However, both of the cells
containing tap water seeped; total cumulative seepages were 623 ml and
1299 ml, respectively, over 7.5 years.
Dismantling of Cells and Recovery and Testing of Liners--
On removal from the exposure cells, the individual asphalt concrete
liner specimens were cored and subjected to the following tests:
- Permeability.
- Voids content.
- Unconfined compressive strength.
- Asphalt viscosity following extraction.
The results of these tests are presented in Table 26.
Acidic wasteThe hydraulic asphalt concrete (HAC) liners in the two
cells containing the acidic waste failed and were removed and tested
after 40 and 199 days of exposure. As indicated above, the surface of both
liners was rough and spongy and much of the rock aggregate had dissolved
due to reaction with the waste which contained some hydrofluoric acid.
93
-------
TABLE 26. ASPHALT CONCRETE (HAC) AFTER EXPOSURE TO HAZARDOUS WASTES3
Type of waste
Name and number of waste
Cel 1 number
Exposure time, days
Acidic
"HN03-HF-HOAC"
(W-9)
C-31
40
C-26
199
Lead
(W-14)
C-27
192
Pesticide
"Weed killer"
(W-ll)
C-23
569
HAC concrete13
Coefficient of permeability, cm s~! 1.3 x 10~8 2.6 x 10~8 2.4 x 10"9
Density, g/cm3 2.322 ... 2.294 ... 2.351
lb/ft3 145.0 ... 143.2 ... 146.8
Voids content, % volume 4.6 ... 5.8 ... 3.4
Compressive strength, psi 268 162 234 21C 237
Retention of original
strength, % ... 60 87 8 88
Extracted asphalt
Depth of slice from top, cm
Viscosity6 at 25°C and 0.01 s-1, MP
Shear susceptibility
Penetration at 25°C, calculatedS
0-1
4.90
0.10
48
2-3
1.78
0.70
71
0.3d-l
3.66
0.09
53
2-3
1.22
0.13
87
0-1
f
*
2-3
1.78
0.14
75
2
0
* *
.73
.11
60
2
0
0-1
.55
.03
58
2-3
1.78
0.14
75
aThe effect on asphalt of exposure to weather at Richmond Field Station for 1,485 days (4.07 years)
was measured. Asphalt extracted from top 6 mm (0.25 in.) of weather-exposed piece, cut from the same
slab from which liner test specimens were cut, had a viscosity at 25°C and 0.01 s~l shear of 15.8 MP
and a calculated penetration at 25°C of 28.
^Thickness of liner specimen: 6.3 cm (2.5 in.).
cCompressive strength measured using "Pocket Penetrometer" because cores were too soft to hold shape
and be tested. The viscosity measured on the recovered asphalt does not represent the very low vis-
cosity of the asphalt binder of the concrete in the in-place liner; the binder contained hydrocarbon
absorbed from the waste. This hydrocarbon, along with the extracting solvent, evaporated in the
recovery.
dAsphalt from 0 to 0.3 cm was too hard to test.
eMicro = Caltrans Method 365.
^Asphalt from 0-1 cm was too hard to test.
QCalculated from absolute viscosity at 25°C.
-------
The unconfined compressive strength of the 2-in. cores taken from the
exposed concrete as well as from a piece of the original concrete that had
been retained in the laboratory for 16 months are reported in Table 26.
The cores cut from liners exposed to acid waste had lost strength signi-
ficantly in comparison with the laboratory-aged concrete.
The consistency of the asphalt was measured to determine the effect of
aging after exposure to the waste. The viscosity of asphalt extracted from
different depths of the liner was determined and the results are reported
in Table 26.
The asphalt taken from the top surface upon drying was hard and
powdery and had such a high viscosity that it could not be measured. The
asphalt extracted from the first centimeter of depth was considerably
harder than the original material and harder than that taken from deeper in
the pavement. On the other hand, it was essentially the same as that of
material which had been retained in a can in an uncompacted form or had
been exposed to air in the compacted form for about 16 months. It appears
that the low permeability to air of asphalt concrete has protected the
inner asphalt in the compacted concrete.
Alkaline WasteThe liner in one cell containing the "Spent caustic"
waste leaked early. The tank was emptied, filled with water, and the
base was pressurized with air. Bubbles rose to indicate the spot of
leakage. The small holes were repaired with a coating and the cell was
reloaded with "Slopwater" waste and returned to test. Neither liner
specimen has been recovered at this time (July 1983) to determine changes
in its properties.
Lead HasteOne cell containing lead waste seeped and was dismantled
after 192 days of exposure. The asphalt concrete liner from this cell
absorbed large amounts of the organic fraction in the waste and became very
soft, almost a slush. It could not be lifted from the base without sag-
ging and therefore was slid off of the gravel onto a piece of plywood.
The asphalt had softened and some had flowed down into the base and covered
the top surface of the white gravel below. Tests with a pocket penetro-
meter yielded:
Unconfined
compressive
strength Location
1.3 kg/cm2 Between edges of crust
3.7 kg/cm2 On top of crust
1.5 kg/cm2 In a soft area
Cores were then cut by hand with 2-in. brass tubing applying only slight
pressure and rotation. The cell had to be tipped on its side to remove the
cores which fell apart when placed in bottles.
Pesticide wasteThe cell with the pesticide waste was removed after
569 days of exposure. The liner remained in satisfactory condition,
95
-------
retaining its compressive strength and showing only slight hardening on
aging.
Normal aging of asphalt concrete--Two-inch specimens were also
molded of the hydraulic concrete which had been retained in closed cans in
uncompacted form. The unconfined compressive strength of these test
specimens was probably higher than the original material because of the
higher viscosity. The strength of this concrete which was retained after
immersion in water was also relatively high and the percentage loss in
strength during immersion was not as great as experienced by concrete
exposed to the waste (Table 27).
Bentom'te-Sand Mixtures
Selection of Combinations of Wastes and Liners--
Ten liner specimens based on bentonite-sand mixtures were prepared.
Eight were based on a treated bentonite (Bentonite A) from one manufacturer
and two on a treated bentonite (Bentonite B) from a second manufacturer.
The cells with liners based on Bentonite B were loaded with the lead waste,
"Slurry oil" waste, "Oil Pond 104" waste, and the pesticide waste. The two
cells with liners based on Bentonite A were loaded with pesticide waste.
In the compatibility tests that were run to determine the waste liner
combinations, the acidic and alkaline wastes broke through the bentonite in
a relatively short time. As a consequence, these wastes in combination
with the bentonites were not included in the primary exposure test.
Monitoring the Cells--
Of the ten cells with liners of modified bentonite, measurable seepage
occurred in seven cells, one of which failed allowing the waste ("Oil Pond
104") to come through the liner. Seepage was collected regularly, mea-
sured, and analyzed for solids, pH, and electrical conductivity. The level
of waste in the tank was also monitored. Irrespective of the type of waste
above the two types of bentonite liners, the quality of the seepage was not
greatly different. The seepage in the cells containing the pesticide waste
was approximately twice as great for the two Bentonite A liners as for the
two Bentonite B liners. Monitoring data for the cell that contained the
liner of the Bentonite A-sand mixture and the "weed killer" waste are
presented in Table 28. The electrical conductivity data were erratic and
did not correlate with the data on total dissolved solids.
Dismantling of Cells
Two cells with Bentonite B-sand liners were dismantled; one cell
contained "Oil Pond 104" waste (after 982 days of exposure) and the other
cell contained lead waste (after 986 days of exposure). When the spacers
containing the bentonite-sand mixtures were opened and the liners sampled,
it was found that there had been considerable "fingering" of the wastes
into these liners. The oil wetting front was very irregular and mostly
vertical cracks were observed; oil penetrated along these cracks all the
96
-------
TABLE 27. DENSITY AND OPPRESSIVE STRENGTH OF ASPHALT CONCRETE (MAC)
Sample description
Unconfined compressive
Voids strength at 25°C
Specific content, Retention of
gravity % psi strength, %a
Laboratory compacted briquets
prepared December 1976 from
uncompacted concrete retain-
ed in closed can since August
1975. Tested dry.
Average
2.352
2.351
2.256
2.320
3.4
3.2
7.3
4.6
491
453
513
486
Tested after 24 h
in 60°C water.
immersion
Average
2.331
2.343
2.347
2.340
4.3
3.8
3.6
3.9
359
365
356
360
74
75
72
74
Core cut from sample compact-
ed in August 1975 and retain-
ed in lab until December 1976.
2.323
4.6
268
Cores cut from liner in cell
exposed to strong acid waste
for 3 months, retained under
water until tested.
Average
169
154
163
162
63
57
61
60
Detentions for briquets tested after immersion in 60°C water bath
reported as percent of average strength of briquets tested dry. Re-
tentions for cores tested after acid waste exposure reported as percent
of strength of unexposed core.
way to the bottom of the specimen. Upon dismantling one cell and trying
to remove the liner specimen as a whole, it collapsed, breaking along
these cracks. This is evidence that, even in a wet state, the bentonite
did not succeed in providing enough cohesion to the sand mass to withstand
its own weight. No channeling of the waste at the walls of the spacers was
evident.
97
-------
TABLE 28. MONITORING OF CELLS - COLLECTION AND ANALYSIS OF SEEPAGE FROM CELL
WITH BENTONITE A-SAND MIXTURE AND PESTICIDE WASTE (W-ll)
OO
Time, days
Date
3-26-77
11-11-77
5-10-78
9-15-78
4-27-79
2-4-80
4-21-80
9-15-80
11-7-80
2-6-81
5-7-81
8-7-81
11-6-81
2-8-82
5-7-82
8-6-82
11-10-82
2-8-83
5-3-83
Incremental
0
230
180
124
224
77*
147
53
91
90
92
90
94
90
91
96
90
87
Elapsed
0
230
410
534
758
1118
1265
1318
1409
1499
1591
1681
1775
1865
1956
2052
2142
2229
Amount, mL
Incremental
900
610
460
728
^U 1 1 cV-U 1 Ull
174
lllc
260
310
339
372
332
200
270
475
218
0
380
Cumulative
f~o1 1
LL 1 1
900
1510
1970
2698
lost - bag repl
2872b
2983b
3243b
3553b
3892b
4264b
4596b
4796b
5066b
5541b
5759b
5759b
6139b
Total
dissolved
solids,
%
f i 1 1 oH
1 1 1 1 cu
0.27
0.27
0.31
0.28
0.29
0.30
0.29
»
0.30
0.30
pH
8.9
8.2
7.2
6.6
6.4
6.4
6.6
6.1
5.9
6.1
6.1
6.0
5.8
5.8
5.9
Waste level
below tank
top, in.
»
2.6
2.6
3.3
4.0
*
4.5
1.5
4.9
5.0
5.5
5.4
5.7
5.8
6.0
6.0
6.2
aTime interval before collection on April 21, 1980 was 77 days; earlier collections between
April 27, 1979 and February 4, 1980 were lost.
Cumulative amount based on all available data but does not include estimates of lost col-
lections between April 27, 1979 and September 15, 1980.
cMost of collection lost.
-------
This type of liner is probably not satisfactory for these types of
waste. The use of a soil cover on the bentonite layer to produce an over-
burden would probably reduce the fingering effect.
Migration of Constituents--
The Bentonite B-sand liner was sampled in a fashion similar to that
used in the sampling of the soil. The samples of the Bentonite B-sand
mixture that had been exposed to the lead waste were submitted to H.E.
Doner at the University of California, Berkeley, for analysis and trace
metals distribution. Results are presented in Table 29.
TABLE 29. ELEMENTAL ANALYSIS AVERAGED OVER ALL DEPTHS
FOR BENTONITE B-SAND LINER
Metal concentration, pg/g oven-dried soil
Treatment
Lead waste
Cadmi urn
0.19
Ch romi urn
3.17
Copper
7.1
Me rcu ry
0.008
Nickel
1.7
Lead
9.0
The pH of the Bentonite B-sand mixture was between 8.0 and 8.3 with
the higher value in the top 4 cm. This high value may be due to the
presence of calcareous material.
Discussion of Results on Modified Bentonite Liners--
Even though there had been some flow through the liner, the distribu-
tion of the heavy metals throughout the different depths of the liner was
uniform, which indicates that there was no contamination by the waste.
Therefore, the data were averaged as shown in Table 29.
Soil-Cement
Selection of Combinations of Wastes and Liners--
The ten liner specimens of 4-in. thick soil-cement were placed in
exposure to five wastes, as shown in Table 30.
TABLE 30. WASTES USED IN EXPOSURE TEST OF SOIL-CEMENT
Waste identification
Type
Alkaline waste
Lead waste
Oily waste
Pesticide waste
Name
"Spent caustic"
"Slurry oil"
"Oil Pond 104"
"Weed killer"
Matercon
serial
number
(W-2)
(W-14)
(W-15)
(W-5)
(W-ll)
Number
of
cells
2
2
2
2
2
99
-------
Due to the known sensitivity of the soil-cement to acid, the acidic
waste "HN03-HF-HOAc" was not included in the exposure test. This sen-
sitivity was confirmed in compatibility tests (Haxo et al, 1977).
Monitoring of Cells--
During the first year of exposure, no seepage occurred in any of the
ten cells containing soil-cement liners. The first five specimens were
dismantled for testing after 328 to 527 days of exposure. No seepage
through the soil-cement liner specimens in the remaining five cells has
occurred in more than six years, except for a small amount (60 ml) in the
cell containing "Oil Pond 104" waste.
Effect of Exposure on Properties--
One set of the soil-cement lining materials was recovered after 328
to 625 days of exposure to the five wastes and the individual liners were
cored and tested for compressive strength. In all cases, compressive
strength of the exposed soil-cements was greater than that of the corres-
ponding unexposed material as shown in Table 31. Some blistering occurred
in the epoxy-asphalt coating (Seal C) that was applied to one-half the
surface of each specimen.
TABLE 31. COMPRESSIVE STRENGTH OF SOIL-CEMENT LINERS
AFTER EXPOSURE TO DIFFERENT WASTES
Exposure
Unexposed3, tested dry
Unexposedb
"Weed killer" waste
"Spent caustic" waste
Lead waste
"Oil Pond 104" waste
"Slurry oil " waste
Matrecon
waste
serial
number
W-ll
W-2
W-14
W-5
W-15
Exposure
t i me ,
days
0
0
ca 560
627
627
627
328
Compressive
strength,
psi
1321
604
159?
1639
1363
1798
1687
Percent
of dry
unexposed
soil -cement
46
121
124
103
136
128
aStored in plastic bag, but had dried out.
^Similar core to (a); tested after immersion in water at room tempera-
ture for one week.
100
-------
Analyses and Trace Metals Distribution--
Cores were also cut from the exposed soil-cement liner specimens for
submission to H.E. Doner of the University of California, Berkeley, for
determination of the trace metals distribution. The cores were sectioned
dry with a diamond saw at three different depths and then treated similarly
to the soil samples (see above).
The results of the analyses are presented in Table 32. As noted in
the table, the values are similar for all four of the exposed soil-cement
liners which indicates that the values equal those for unexposed soil-
cement and that there was no contamination by the wastes.
TABLE 32. ELEMENTAL ANALYSIS AVERAGED OVER ALL DEPTHS FOR SOIL-CEMENT
Metal concentration, yg/g oven-dried soil
Exposure Cadmium Chromium
"Spent caustic" waste
Lead waste
"Oil Pond 104" waste
"Slurry oil" waste
Discussion of Soil -Cement
0.02
0.02
0.02
0.02
Liner
27.4
26.6
26.8
27.5
Results--
Copper
27.8
28.3
27.5
28.4
Mercury
0.16
0.16
0.18
0.17
Nickel
38.4
38.0
37.9
39.4
Lead
22.2
20.2
20.7
21.5
As evidenced by the lack of seepage, the soil-cement had very low
permeability and was quite compatible with the specific wastes to which it
was exposed, i.e. the oily, alkaline, and pesticide wastes. The acidic
waste had been eliminated in the preliminary compatibility tests.
SPRAYED-ON ASPHALT
Preliminary Compatibility Tests
The membrane based on emulsified asphalt sprayed on a nonwoven fabric
was placed under three of the six wastes: pesticide, "Spent caustic," and
lead. Two cells with each waste were placed in exposure. The acid waste
was excluded because of the severe hardening it caused the asphalt in
preliminary exposure tests and the oily wastes were excluded because of the
high mutual solubility of the asphalt and such wastes. Later in the
program the remaining four cells were loaded with deionized water and with
5% aqueous solution of NaCl for use in immersion testing.
Monitoring of Cells
No seepage of the original six cells occurred up to 489-671 days of
exposure when the first group of cells was dismantled to assess the effects
of respective exposures on the liners. Subsequently, the second cell with
101
-------
"Spent caustic" waste was dismantled because of the failure of the cell
tank due to corrosion by the salt-caustic mixture. Also, after 780 days of
exposure the liner in one of the cells with 5% NaCl solution began to leak
and has continued to leak slowly. At the time of the writing of this
report (July, 1983) this has amounted to 966 additional days.
Dismantling of Cells and Recovery and Testing of Liners
After 489-671 days of exposure, three cells with pesticide, "Spent
caustic," and lead wastes were dismantled and the liners recovered and
tested. Two additional cells, one with "spent caustic" waste and the other
with lead waste, were dismantled after 1480 and 1348 days, respectively,
and the liners recovered and tested. Results are reported in Table 33.
The volatiles content of the liners exposed to the "Spent caustic"
waste and the lead waste increased significantly. Presumably, the vola-
tiles were principally water.
A sample of each liner was extracted and the viscosity of the re-
covered asphalt determined. There is some indication that, for the long
exposure, the asphalt hardened after having softened somewhat during the
shorter term exposures.
As of May 1983, the remaining five liners were still being exposed to
the pesticide waste, deionized water, and NaCl solution. Four were func-
tioning satisfactorily; however, the fifth with 5% NaCl solution is leak-
ing. The electrical conductivity of the effluent is similar to that of
the liquid above the liner.
This type of liner appears to be compatible with water and with dilute
waste waters but is questionable for use with oily wastes, acid wastes, and
possibly other wastes. It definitely requires compatibility testing with
the specific waste which is to be impounded.
POLYMERIC MEMBRANES
The exposure testing of polymeric membranes formed the principal part
of this project. As indicated in Section 5, a large number of polymeric
membranes were candidates for the test. Based upon their properties, the
eight membranes listed in Table 34 were selected for the primary exposure
test. It had originally been planned to include only nonreinforced mem-
branes in the program but, because of product unavailability at the time
the project was started, two fabric-reinforced membranes were substituted.
In the planning stage, it was recognized that several of these lining
materials would not be compatible with some of the wastes that were avail-
able for the test program. Because only a limited number (144) of cells
were fabricated for the project and, because it was desired to include only
those combinations of liners and wastes that would have reasonable dura-
tions of exposure, preliminary compatibility tests were deemed necessary.
By eliminating some combinations which were expected to fail, it was
possible to test the maximum number of different combinations for the
desired periods of exposure.
102
-------
TABLE 33. EMULSIFIED ASPHALT SPRAYED ON NONWOVEN FABRIC AFTER EXPOSURE TO HAZARDOUS WASTES3
o
oo
Waste type
Waste name
Matrecon waste
Exposure time,
serial number
days
Alkaline
"Spent
caustic"
(W-2)
None 671 1480
Lead
(W-4)
656 1348
Pesticide
"Weed
killer"
(W-ll)
487
Asphaltic liner:
Volatiles content of liner, %
Water vapor permeability^,
metric perm cm
Extracted asphalt;
Viscosity at 25°C, P x 106
0.26
6.7 x 10-2
12.9 15.3
18.6 21.5
1.45
at 0.05 s-1
at 0.01 s-1
at 0.001 s-1
Shear susceptibility
Penetration0 at 25°C
6.1
5.9
5.7
-0.02
41
4.40
4.22
4.00
-0.02
47
8.14
8.03
7.72
-0.02
37
5.52
5.56
5.92
0.02
43
6.49
6.91
7.53
0.04
40
5.4
5.4
5.4
0.00
43
aLiner covered with 1.5 in. of silica sand on which the waste was placed.
bASTM E-96, Method BW.
Calculated from viscosity at 0.05 s'1 by formula of Carre and Laurent (Association Francaise
des Techniciens du Petrole, Bulletin No. 157, pp 1-54, January 31, 1963):
(Pen)2'6 = 9.5 x 1010
-------
Note: The original design of the project was to expose 12
different liners including soil, admix, sprayed-on, and
polymeric membrane liners exposed for two time periods in
six different waste sludges.
TABLE 34. POLYMERIC MEMBRANE LINERS SELECTED FOR EXPOSURE
IN HAZARDOUS WASTES
Thickness,
Polymer mil
Butyl rubber (IIR), fabric-reinforced 34
Chlorinated polyethylene (CPE) 32
Chlorosulfonated polyethylene (CSPE),
fabric-reinforced 34
Elasticized polyolefin (ELPO) 25
Ethylene propylene rubber (EPDM) 50
Neoprene (polychloroprene - CR) 34
Polyester elastomer (PEL) 8
Polyvinyl chloride (PVC) 30
Preliminary Compatibility Testing
A preliminary compatibility test was run on the selected liners plus
some additional liners in the available wastes. This test is described in
the Interim Report (Haxo et al, 1977). Basically, the test involved the
immersion of strips of different lining materials in the different wastes
and observing the effects on the strips with time. Major properties that
were of importance were the swelling of the membranes in the different
wastes and the visual and general effects upon properties as would be
measured essentially by hand. Table 35 summarizes the preliminary com-
patibility tests that were performed prior to selection of membranes to
expose as primary liners in the cells. The table also includes data on the
asphaltic liner materials and the various sealing materials that were being
considered for use in the installation of the liner specimens in the cells.
Materials that swelled inordinately or became sticky were eliminated. The
final selection of the combination of wastes and polymeric membranes is
given in Table 36.
In addition to those combinations of wastes and liners which were
tested in two cells, additional single cells were prepared to use for the
immersion testing of polymeric materials in additional wastes. These
combinations are also shown in Table 36.
Monitoring the Cells
During exposure, the cells were checked for seepage below the liners
and for changes in the waste levels in the tanks above the liners.
104
-------
TABLE 35. EFFECT OF IMMERSION IN WASTE ON MEMBRANE LINERS AND SEALING MATERIALS - PRELIMINARY SCREENING STUDY3
Wastes
Material Acidic Alkaline
Ident!- "HN03-HF- "Slop
fiction "HFL" HOAc" water"
Composition number0 (W-10) (W-9) (W-4)
Polymer lining materials
Butyl rubber (IIR) 22 NVC NVC NVC
24 NVC NVC NVC
44
57Rd NVC NVC NVC
Chlorinated
polyethylene (CPE) 12d NVC NVC NVC
38 NVC NVC NVC
39R NVC NVC NVC
48R
73R NVC NVC NVC
Chlorosulfonated
polyethylene (CSPE) 6Rd NVC NVC NVC
50RC
55 NVC NVC NVC
Elasticized
polyolefin (ELPO) 36d NVC NVC NVC
41 NVC NVC NVC
Ethylene propylene
rubber (EPDM) 8 NVC NVC NVC
26d NVC NVC NVC
Neoprene (CR) 9 CC SCR CC
37 NVC NVC NVC
42R NVC RVD NVC
43Rd
47R
56R NVC NVC SHD
74R NVC NVC f
Polyester elastomer (PEL) 69 NVC NVC g
75d NVC NVC g
Polyvinyl chloride (PVC) 10 CC NVC HDS
11 NVC NVC HDS
17 NVC NVC HDS
40 NVC NVC HDS
49R
59d NVC NVC HDS
67 NVC NVC HDS
71R NVC h HDS
Polyurethane 45R ... ... ...
46R
51R
70R CC NVC CC
72R CC NVC CC
Asphaltic membranes
Coal tar pitch + PVC 52 NVC NVC HDS
Emulsified asphalt on
nonwoven fabric 58 NVC SCR, BLS NVC
Sealing materials
Butyl caulk 63 NVC NVC NVC
Neoprene sponge 34 NVC SCR SHR
Polyurethane caulk 64 ... RVD SFT-U2
Polysulflde caulk 66 NVC SFT-1S2 SCR
Teflon sponge rod 68 NVC NVC NVC
dBased on Table 14 from the Interim Report (Haxo et al , 1977); the
is an estimated percent increase in area of that portion of strip
^R - fabric-reinforced; RC = fabric-reinforced and crosslinked.
cBlended to make W-14, lead waste.
dMater1als Incorporated 1n cells as primary liners.
"Spent
caustic"
(W-2)
NVC
NVC
NVC
NVC
NVC
NVC
*
NVC
NVC
. * i
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
»
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
...
...
...
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
unit used
immersed.
eComplete loss of tear strength.
^Neoprene in satisfactory condition but reinforcing fabric dissolved.
9Black rubs off, indicating possible dissolving of the liner.
n0.10-in. swell 1n each direction, curled, and delaminated.
KEY TO OBSERVATIONS
ABS - Absorbed waste.
BLS - Blistering of surface.
Lead Oily
Low Pb
washing
(W-8)c
NVC
NVC
NVC
NVC
NVC
NVC
*
BLS
NVC
i <
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
...
'cc
NVC
NVC
NVC
NVC
SHR
NVC
NVC
NVC
KEY TO
CC -
HDS -
NVC -
REV -
RVD -
SCR -
SFT-1 -
SFT-2 -
SHD -
SHR -
Gasoline "Weed
wash water oi 1 "
(W-3)c (W-7)
NVC 68
NVC 91
76
NVC 67
NVC RVD
NVC RVD 92
NVC RVD
RVDe
NVC
NVC RVD
6
NVC
NVC 49
NVC 42
NVC 75
NVC 90
NVC 111
NVC 67
NVC REV
10
6
NVC 100
NVC NVC
NVC 12
NVC 18
NVC NVC
NVC NVC
NVC +11
NVC +24
+3
NVC +26
NVC +5
NVC CC
50
44
2
NVC 33
NVC 28
NVC 17
NVC RVD
NVC RVD
SHR 38
BLS SFT-U2
NVC NVC
NVC ABS
OBSERVATIONS, cont 'd
Color change.
Hardened and shrank.
No visible change.
Reverted.
Removed specimen from
because of excessive
ing or disintegration
Surface cracking and
Softened above waste.
Softened 1n waste.
Slightly hardened.
Shrank.
Pesticide
"Weed
killer"
(W-ll)
NVC
...
NVC
NVC
NVC
NVC
NVC
NVC
...
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
NVC
...
>
NVC
NVC
BLS
. . .
SHR
. . .
...
waste
swell -
hardening.
105
-------
TABLE 36. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS
O
CTi
Wastes3
Acidic Alkaline Oily
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Liner
number^
57
77
6
36
26
43
75
59
Number
of
cells
8
10
10
15
8
8
12
15
'HN03-HF- "Slop
"HFL" HOAc" water"
(W-10) (W-9) (W-4)
2
2
2
1 2 1
2
-
2
1 2 1
Spent
caustic"
(W-2)
2
2
2
2
2
2
2
2
"Lead
waste"
(W-14)
2
2
2
2
2
2
2
2
"Slurry
oil"
(W-15)
-
-
-
2
-
-
2
2
"Oil Pond
104"
(W-5)
-
2
2
2
-
2
2
2
Pest-
icide
"Weed "Weed
oil" killer"
(W-7) (W-ll)
2
2
2
1 2
2
2
2
1 2
aMatrecon waste serial number shown below identification.
^Matrecon liner serial number.
-------
No leakage that could be attributed to seepage through the liners or
through seams for periods of up to 56 months occurred in any of the cells.
Leakage occurred in a few cells through the flanges, and some cells con-
taining the acidic wastes began to leak through the tank walls due to
corrosion. This latter failure required dismantling of the cells and
recovery of the test specimens. The level of the waste in the tanks tended
to drop due to evaporation, even though the cells were covered with a
hardboard cover. Either waste or water was added to replenish the quantity
lost due to evaporation. Crystals of the "Spent caustic" waste "crept"
over the top edge of the tanks and encrusted part of the outside wall of
the cells. Crystals formed above the "waterline" of the "Slop water"
waste and did not continue to form up the inner wall as had the "Spent
caustic" waste.
Dismantling of Cells and Recovery of Liners
The dismantling and recovery of the liner specimens is an important
step in exposure testing of lining materials. At this point, the condition
of the exposed lining material becomes visible and the changes that have
occurred since exposure began can be observed. Dismantling involved the
following major steps:
1. Inspection of the cells immediately before dismantling. This step
included the collection, measurement, and analysis of any effluent
that may have seeped through the liner and the measurement of the
waste depth in the tanks.
2. Observation of the condition of the waste and its removal from the
cells. The wastes were removed with as little stirring as pos-
sible so that observations could be made about any stratification
and the settling out of solid constituents. Also, it allowed
observations to be made about the material that was in direct
contact with the liner, that is, the buildup of solids and its
character. At this point some of the liners were photographed.
3. Cleaning the liner and removing solids that had been deposited on
the liner. The liner was then photographed in place.
4. Removal of the tank part of the cell and recovery of the liner.
The liner was inspected both on the surface facing the waste and
the underneath surface facing the glass cloth and the silica
gravel to determine if there were any deposits on the bottom of
the liner. The condition of the glass cloth and the silica was
also checked.
5. Removal and washing of the silica gravel for subsequent measure-
ment of electrical conductivity and pH of the wash water.
6. Photographing the top and bottom of the liner after removal. The
liners were then sealed in polyethylene bags to prevent loss of
volatiles from the exposed specimens which usually absorbed water
and other volatile constituents in the wastes.
107
-------
Note: Unless the specimen is tested within a few days, poly-
ethylene bags are inadequate to prevent loss of volatiles.
Figure 17 shows a sequence of photographs of the recovery of the
polyvinyl chloride specimen (No. 59) exposed to the pesticide "Weed killer"
waste for 500 days. The top photograph shows the liner after removal of
the waste. The deposit on the liner surface is a clay material that was
used as a carrier for the herbicide. The middle photograph shows the liner
after it was cleaned and removed from the cell and shows the imprint of the
gravel beneath the liner. This liner had a volatiles content of 2.3%,
probably mostly water. The photograph also shows the seam which was double
layered. The bottom photograph shows the condition of the silica gravel
and the glass cloth. In this cell, and as occurred with most of the cells
with polymeric membrane liners, the condition of the fabric and the gravel
appeared to be essentially the same as they were at the time the exposure
was started.
Figure 18 shows two photographs of a neoprene liner (No. 43) that had
been exposed to the lead waste for 499 days; it had swelled considerably
during the exposure period. The top photograph shows the liner in place in
the cell after it had been cleaned. The second photo shows the exposed
specimen after it had been removed from the cell. The wrinkling and
distortion that are shown took place after the waste had been removed from
the specimen, at which time the flat-appearing, exposed specimen billowed
and became distorted. This liner had absorbed considerable waste by the
time it was dismantled as indicated by its high volatiles content and its
flabby appearance and feel.
Generally, the dismantling was performed in groups of cells having the
same waste so that the comparisons of the effects of the waste on several
lining materials could be made visually and the handling of the disposal of
the waste would be more convenient. The times of dismantling for each
cell, that is the days after the respective wastes were placed in the cells
and thus the days of exposure, are presented in Table 37.
Testing of the Exposed Polymeric Membrane Liners
After removal from the cells and cleaning, the exposed membrane liners
were visually inspected thoroughly with low-power magnification for any
unusual effects of the waste, such as blistering, del ami nation, surface
deterioration, etc, and then tested as soon as possible. The typical
pattern used for dieing out physical test specimens from the exposed liner
specimen is shown in Figure 19. This type of pattern was initially used
for testing all of the exposed primary liner specimens including the
fabric-reinforced sheeting as well as the sheeting without the fabric
reinforcement. The special dumbbell with the 0.25-in. wide cross section
was used to test the fabric-reinforced sheeting even though it was recog-
nized that this type of test specimen is not appropriate for testing
fabric-reinforced sheeting. This dumbbell is described in more detail
in the subsection of Section 7 regarding measurements of immersed speci-
mens. The tear resistance of the fabric-reinforced sheeting was not
determined, because the short threads pulled out of the specimens.
108
-------
Figure 17. A sequence of photographs showing the recovery of the poly-
vinyl chloride specimen (No. 59) exposed to the pesticide "Weed
killer" waste for 500 days. Fig. 17a shows the liner after the
the waste has been removed. The light colored deposit on the
bottom is a clay that was used as a carrier for the herbicide.
Fig. 17b shows the liner after it was cleaned and removed from
the cell with the imprint of the gravel beneath the liner. The
photograph also shows the seam which was double layered. Fig.
17c shows the condition of the gravel and the glass cloth.
109
-------
C!5
Figure 18. Two photographs of the recovered neoprene liner (No. 43) that
had been exposed to the lead waste for 499 days. Fig. 18a
shows the liner in place after it had been cleaned.
shows the liner exposure specimen after removal from
110
Fig. 18b
the cell.
-------
TABLE 37. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - DAYS OF EXPOSURE
Wastes9
Acidic Alkaline
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
aMatrecon waste serial number
t>Matrecon liner serial number
Numberb
57 R
77
6R
36
26
43
75
59
shown below
"HN03-HF- "Slop
"HFL" HOAc" water"
(W-10) (W-9) (W-4)
505
1218
459
1218
505
1218
2293 505 2300
1217
497
1147
* *
323
509
1565 505 1565
1352
identification.
"Spent
caustic"
(W-2)
526
1249
526
1249
526
1249
526
2677
526
124
526
1237
526
1237
526
1249
"Lead
waste"
(W-14)
499
1339
499
1334
499
1343
499
1343
499
1344
499
1342
499
1342
499
1345
"Slurry
oil"
(W-15)
...
...
...
327
2355
* * «
328
327
Oily
"Oil Pond "Weed
104" oil"
(W-5) (W-7)
...
521
1358
521
1357
521
1357
...
521
1356
521
1357
521
1356
Pesticide
"Weed
killer"
(W-ll)
500
1258
500
1258
504
1258
494
2699
500
1258
494
1257
501
1258
500
1258
; R = fabric-reinforced.
-------
EXPLANATION
Puncture
Tear DieC
Tensile Dumbbell
Volatiles
Adhesion Test
Specimen
Figure 19. Principal pattern used for dieing out the physical test speci-
mens from the exposed primary exposure specimens.
and the polymer coating. In
act independently. The fabric
the polymer coating to break.
nforced sheeting made for use in the lining of
is very low adhesion between the fabric threads
In other words, the fabric and the coatinq can
Most of the fabric-reinforced sheeting made for i
pits and ponds generally has very low adhesion betweei
and the polymer coating. In other words, the fabric and the coating can
>endently. The fabric can break at low elongation without causing
As the primary objective in this project was to determine the effects
of exposures to different wastes on the polymer compound and not on the
fabric, we were concerned with the coating. The effect on the fabric is a
112
-------
separate problem which involves not only the type of fiber but its size
and the weave of the fabric. The use of the two test specimens appeared to
be satisfactory for membranes with less than 10 x 10 epi, such as the CSPE
sheeting (No. 6R) with 8 x 8 epi nylon fabric. With this construction of
membrane, in the tensile test the fabric broke at elongations usually less
than 25%. The CSPE coating compound remained as a continuous sheet, which
ultimately broke at a much higher elongation, e.g. >200 percent. In the
tear test the threads pulled out leaving the coating to tear independently.
It was possible to follow the changes in the coating compound during the
exposure by considering the breaking and tearing of the coating and ne-
glecting the behavior of the fabric.
However, the more tightly woven fabric (22 x 11 epi) with its slight
adhesion to the butyl compound in membrane 57R did not allow the rubber
coating to act separately from the fabric. With this membrane (57R), when
the fabric broke in the tensile test in the transverse direction, the
coating broke almost simultaneously, so the effect of exposure on the
coating could not be assessed. The effect upon the tear values was some-
what similar. As a consequence, tear testing of fabric-reinforced mem-
branes was dropped from the test and 1-in. strips of fabric-reinforced
membranes were used later in the project for assessing the effect of
exposure on tensile properties. In such cases, a different pattern was
used to die out the test specimens as shown in Figure 20.
The principal properties that were measured on the exposed membranes
were:
- Volatiles content.
- Extractables content.
- Hardness.
- Tensile properties in machine and transverse directions, i.e.
tensile strength, elongation at break, and stress at 100% and 200%
elongation.
- Tear strength of unreinforced sheeting measured in machine and
transverse directions.
- Puncture resistance.
- Seam strength in shear and peel modes.
The results of testing the exposed membranes are presented in Appendix
I. These data are presented by individual lining material, by the type of
waste, and for each of the two elapsed times that the liners were exposed.
Data are presented on the properties listed in Table 15, with the exception
of the data on seam strength which are presented in Table 43. Tensile
and tear properties which are measured in both machine and transverse
113
-------
EXPLANATION
Puncture
Volatiles
Tear Die C
Tensile Dumbbell
Adhesion Test
Specimen
Tensile Specimen for
Fabric Reinforced
Sheeting
Figure 20. Pattern used for dieing out the physical test specimens from
the exposed primary specimens with fabric reinforcement. Both
dumbbells and 1-in. strip test specimens were cut and tested in
the second set of exposed specimens.
directions were averaged and the averages were used to develop the reten-
tion data reported; thus, the test results for all the exposed liners can
be compared.
114
-------
Retention of Selected Properties of Liners on
Exposure to Different Wastes
Data on four properties of significance in measuring the effects on
polymeric membrane liners of exposure to wastes are presented in Tables
38, 39, 40, and 41 for the exposed materials for each of the respective
exposure periods shown in Table 37. These properties are percent vol-
atiles, percent extractables, percent retention of stress at 100% elonga-
tion, and percent retention elongation at break. The data show the effect
of the waste at each exposure time on each of these properties. Compari-
sons of the effects of the different wastes on the lining materials can
thus be made. The data also show both the variation in magnitude of the
effects on different polymeric lining materials by given wastes and the
different effects of the different wastes on a given lining material.
Information on the seams and on the retention of seam strength are
given in Tables 42 through 44. Table 42 presents information on the
type of seaming procedures along with information on the fabricator of the
seams. Table 43 presents the results of testing the seam strength of the
specimens measured in shear after their respective exposures, together with
data on the unexposed materials. Table 44 presents results of testing the
strength of the seams in the peel mode. All the data show the strength
values in pounds-per-inch width (ppi) and the locus of failure of the
adhesion test specimen.
The results of the exposure testing of the individual liners are
discussed in subsequent subsections.
Butyl Rubber Membrane--
The butyl rubber membrane (No. 57R) was fabric reinforced with a nylon
scrim of 22 x 11 epi thread count. It had a nominal thickness of 34 mils
with a vulcanized coating compound that contained 23.46% ash, 6.36% ex-
tractables, and 0.29% volatiles. The high ash content reflects the use of
inorganic fillers in the compound. Two sets of specimens of this membrane
were exposed to four wastes:
Acidic waste, "HNOa-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Pesticide waste.
Combinations of the butyl membrane with the oily wastes were not selected
for the primary exposure program as a result of the preliminary compati-
bility testing. The lead waste was included because, given the results of
the compatibility testing, it appeared to contain only a small amount of
oily constituents.
The specimens from the first set were recovered after 500 to 526 days
of exposure and specimens from the second set after 1218 to 1339 days of
exposure.
115
-------
TABLE 38. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - PERCENT VOLATILES^
CTl
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethyl ene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Number0
57R
77
6R
36
26
43
75
59
Original
value,
0.29
0.14
0.51
0.15
0.50
0.45
0.26
0.31
Acidic
"HNOi-HF-
"HFL" HOAc"
(W-10) (W-9)
5.92
11.46
7.82
13.18
4.69
7.18
1.46 3.20
5.26
8.95
12.02
0.39
4.74
9.90 12.08
13.94
Wastesb
Alkal ine
"Slop
water"
(W-4)
...
...
10.83
...
...
. .
18.72
"Spent
caustic"
(W-2)
1.75
1.37
2.32
2.79
4.77
5.77
1.25
1.01
1.27
1.31
4.40
5.67
0.65
0.89
2.34
1.85
"Lead
waste"
(W-14)
2.79
3.53
11.58
19.20
1.08
11.44
1.03
1.53
2.83
5.25
18.01
17.50
2.63
1.72
3.34
4.43
"Slurry
oil"
(W-15)
...
...
...
0.38
4.02
...
...
0.40
0.29
Oily
"Oil Pond "Weed
104" oil"
(W-5) (W-7)
...
3.69
10.11
7.51
10.25
2.15
5.12
...
12.99
21.31
1.27
2.59
1.70
4.19
Pesticide
"Weed
killer"
(W-H)
4.10
4.79
4.99
7.91
8.00
9.73
0.13
0.58
3.34
6.29
11.29
13.63
0.60
2.92
2.30
3.61
Respective durations of exposure are presented in Table 37.
^Matrecon waste serial number shown below identification.
cMatrecon liner serial number; R = fabric reinforced.
-------
TABLE 39. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - PERCENT EXTRACTABLES3
wastesb
Acidic Alkaline
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethyl ene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Numberc
57R
77
6R
36
26
43
75
59
Original
value,
6.36
9.13
3.77
5.50
22.96
13.69
2.71
35.86
"HN03-HF- "Slop
"HFL" HOAc" water"
(W-10) (W-9) (W-4)
::: 8:65 :::
10.09
9.41
... 4 '.62 ...
5.40 5.40 1.70
7.09
21.36
...
10.77
13.36
34.42 16.68 10.40
18.58
"Spent
caustic"
(W-2)
7-.B6
9.10
4.77
5.77
5 '.96
23.95
i3:69
3.85
3.31
34.62
35.61
"Lead
waste"
(W-14)
7.75
7.86
7.31
7.24
3.52
5.95
5.66
8.06
22.27
26.01
12.54
12.15
2.98
5.35
33.47
22.47
"Slurry
oil "
(W-15)
...
...
...
13.94
23.88
...
»
9.91
39.63
Oily
"Oil Pond "Weed
104" oil"
(W-5) (W-7)
...
17.00
9:45 :::
13.72
20.74
...
15.86
5.63
7.28
32.62
29.99
Pesticide
"Weed
killer"
(W-HJ
5.15
7.62
9.72
9.41
4.13
5.39
7.14
6.86
23.13
25.20
13.25
16.14
5.15
5.83
35.27
33.39
Respective durations of exposure are presented in Table 37.
^Matrecon waste serial number shown below identification.
cMatrecon liner serial number; R = fabric-reinforced.
-------
TABLE 40. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - PERCENT RETENTION OF ELONGATION AT BREAK3
CO
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Numberc
57R
77
6R
36
26
43
75
59
Original
value,
42d
402
242
665
450
320
575
375
Ac i d i c
"HNOo-HF-
"HFL" HOAc"
(W-10) (W-9)
60
645
89
89
90
79
98 99
96
97
94
::: :::
4
88 82
71
Alkal ine
"Slop "Spent
water" caustic"
(W-4) (W-2)
60
219
107
88
70
65
88 100
97
102
95
98
95
86
86
3 102
97
Wastes
"Lead
waste"
(W-14)
119
167
101
83
107
77
92
94
100
106
76
75
98
90
95
93
b
Oily
"Slurry "Oil Pond "Weed
oil" 104" oil"
(W-15) (W-5) (W-7)
... ... ...
98
88
103
72
96 86
97 78
86
92
77 95
92
90 85
85
Pesticide
"Weed
killer"
(W-ll)
"143
100
100
89
112
85
101
97
100
104
93
83
96
87
101
95
Respective durations of exposure are presented in Table 37.
^Matrecon waste serial number shown below identification.
cMatrecon liner serial number; R = fabric-reinforced.
dValue reported is elongation at ultimate break with respective retention values. Fabric in sheeting retained its original elongation (25J).
-------
TABLE 41. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - PERCENT RETENTION OF STRESS AT 100% ELONGATION3
Wastes'3
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethyl ene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Number0
57R
77
6R
36
26
43
75
59
Original
value,
psi
(d)
900
937
922
357
460
2585
995
Acidic
"HN03-HF-
"HFL" HOAc"
(W-10) (W-9)
...
97
113
106
112
98 92
98
81
70
...
...
153 200
249
Alkaline
"Slop "Spent
water" caustic"
(W-4) (W-2)
...
82
129
165
200
97 87
87
88
108
90
95
101
109
99
115
"Lead
waste"
(W-14)
...
56
71
85
118
95
104
84
80
53
61
88
82
103
"Slurry
oil"
(W-15)
...
...
...
70
60
...
...
77
113
Oily
"Oil Pond "Weed
104" oi 1 "
(W-5) (W-7)
...
53
62
63
96
61
71
...
50
42
94
85
152
174
Pesticide
"Weed
killer"
(W-1I)
...
94
113
90
118
104
,91
89
87
62
54
95
96
100
137
Respective durations of exposure are presented in Table 37.
^Matrecon waste serial number shown below identification.
cMatrecon liner serial number; R = fabric-reinforced.
dl)nexposed material broke at less than 1005! elongation.
-------
TABLE 42. SEAMS IN POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS
Polymeric membranes
Liner
number
Method of seaming
Seam
width,
in. Fabricator
Butyl rubber
57R
Chlorinated polyethylene 77
Chlorosulfonated poly-
Vulcanizable adhesive furnished by supplier
of liner
Solvent weld with mixture of 1 part toluene
and 1 part tetrahydrofuran
Matrecon
Matrecon
ethyl ene
Elasticized polyolefin
Ethyl ene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
6R
36
26
43
75
59
Adhesive furnished by liner supplier
Heat sealed
Adhesive and gum tape furnished by supplier
Cement and lap sealant furnished by supplier
of liner
Heat sealed
Solvent weld using mixture of 2 parts tetra-
hydrofuran and 1 part cyclohexanone
2
0.5
2
2
0.5
2
Matrecon
Supplier
Matrecon
Matrecon
Supplier
Matrecon
aAll seams were allowed to age at least a month before being tested or covered with wastes.
-------
TABLE 43. EXPOSURE OF POLYMERIC M£WRANE LINER SPECIMENS IN PRIMARY CELLS - EFFECT ON SEAM STRENGTH MEASURED IN SHEAR MODE"
Seam strength In ppl
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Number*
57R
77
6R
36
26
43
75
59
Original
value,
ppl
>84.8d
48.39
62.19
28.89
39.01
45.7"
21.29
>69.1d
Method
of
seaming
Cement6
Solvent
Cement
Heatk
Cement6
Cement6
Heatk
Solvent
Acidic
"HNOi-HF-
"HFL" HOAc"
(M-10) (W-9)
... >67.8d
... >73.3d
27.1"
39.8"
52.79
57.49
32.49 29.29
32.09
47.9'
::: :::
69.29 74.79
79.0"
Alkaline
"Slop "Spent
water" caustic"
(H-4) (W-2)
>74.4f
>78.6d
41.5h
46.0"
64. 01
>76.3d
31. 3h 28.99
31.49
39. 11
45.9"
'.'.'. >58!5d
::: :::
71.61 50.49
63.69
after exposure to different wastes0
"Lead
waste"
(W-14)
64.69
>70.7d
26.3'
26.39
58. 2 J
66.69
26.09
29.09
32.2}
13.91
2?!l"
25.'2"
>16.7d
53.19
45.09
"Slurry
oil"
(IMS)
:::
...
...
21. 7d
24.49
...
...
>18.8d
59.39
Oily
"Oil Pond "Weed
104" oil"
(W-5) (H-7)
...
16.49
25.59
60. 5h
60.3d
M9.39
18.39
...
24. 8P
14.69
28.29
>14.6d
60.99
77.19
Pesticide
"Heed
killer"
(H-ll)
69. lh
>68.8d
>38.8d
>44.5d
>61.3d
65. 7h
26.59
32.59
46.5'
44.4'
>23.7d
34. 9h
26.59
21. 9h
46. 01
60.49
»Strip specimen 1 In. wide; Initial jaw separation, 4 In.; rate of jaw separation, 2 1pm. All seams fabricated by Matrecon following manufacturers' recom-
mendations, except where otherwise noted. Value for seam strength is reported in pounds-per-inch-wldth (ppi). A "greater than" symbol is used to indicate
that the strength of the seam Itself Is greater than the value reported. See Table 37 for durations of exposure.
°Matrecon waste serial number shown below Identification.
cHatercon liner serial number; R = fabric-reinforced.
Specimens failed at clamp edge.
eLow-temperature vulcanizing adhesive.
fSpecimens failed outside of seam area and not In the clamped area.
9Specimens failed at seam edge.
"One specimen failed at seam edge; the other specimen failed in the clamped area.
'One specimen failed at seam edge; the other failed outside of seam area and not In the clamped area.
JOne specimen failed outside seam area; the other failed in seam area which had been separated.
''Seam fabricated by supplier.
'Specimens failed in adhesive.
"One specimen failed at seam edge; other failed In adhesive.
"Specimens failed in bond between adhesive and liner surface.
°0ne specimen failed at clamp edge; other failed outside of seam area and not in clamped area.
POne specimen failed at clamp edge; other failed in bond between adhesive and liner surface.
ITwo specimens failed outside seam area; one specimen failed at clamp edge; two failed at seam edge.
-------
TABLE 44. EXPOSURE OF POLYMERIC MEMBRANE LINER SPECIMENS IN PRIMARY CELLS - EFFECT ON SEAM STRENGTH MEASURED IN PEEL MODE3
ro
ro
Seam strength in ppi
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
NumberC
57R
77
6R
36
26
43
75
59
Original
value,
ppi
8.QO
21.49
23. 2J
21. 01
4.9k
8.2"
20.89
15.29
Method
of
seaming
Cement6
Solvent
Cement
Heatm
Cement6
Cement6
Heat"1
Solvent
Acidic
"HNO^-HF-
"HFL" HOAc"
(W-10) (W-9)
3.2f
4.5f
17.99
19.09
14. lf
12. 5k
22. 61 21. 51
22. 01
5.9k
...
23. 9r 28.4s
34.09
Alkal me
"Slop "Spent
water" caustic"
(W-4) (W-2)
8.5f
4.1f
21.99
21. Oh
21. 3f
28. 4f
22. 01 19. 81
22. 01
4.5k
5.4K
8.8"
10.8"
...
9.8r 21.49
14.89
after exposure to different wastes0
"Lead "Slurry
waste" oil"
(W-14) (W-15)
7 8f
5.3f
17.39
13.79
26. 4J
21. 5k
19. 81 18. 71
22. 21 18. 61
3.5k
2.3k
3.3"
2.2"
17.4° 18. 21
18. 3P
19.0s 20.39
16. 4r
Oi ly
"Oil Pond
104"
(W-5)
. . .
14. 31
11.49
16. 5f
15. Of
M4.51
14. 91
...
...
2.1"
3.6"
18. 81
16.29
23.1s
22. Or
Pesticide
"Weed "Weed
01 1 " ki 1 ler"
(W-7) (W-ll)
10. 9f
3.6f
20.09
16.29
21.3f
15. lf
20.91
23. 21
5.0k
5.0k
7.6n
4.3n
20. 3!
19. 51
18.19
23. Or
aStrip specimen 1-in. wide; initial jaw separation, 2 in.; rate of jaw separation, 2 ipm. Value reported in pounds-per-inch-width (ppi) is average after
initial peak, except where otherwise noted. All seams fabricated by Matrecon following manufacturers' recommendations, except where otherwise noted. See
Table 37 for durations of exposure.
''Matrecon waste serial number shown below identification.
cMatercon liner serial number; R = fabric-reinforced.
^Specimens failed in adhesive.
6Low-temperature vulcanizing adhesive.
^Specimens failed by a combination of failure in the adhesive and in delamination of the lining material.
9Specimens failed at bond between the two 1iner sufaces.
^Specimens initially failed at bond between the two liner surfaces, then failed catastrophically at the line of peel in the course of the test.
""One specimen failed catastrophical ly at the line of peel shortly after it began to peel; the other failed at bond between the two liner surfaces.
JOne specimen failed by delamination of lining material; the other by failure in the adhesive.
Specimens failed in the adhesive.
'Specimens failed catastrophically across the width of the specimen at the line of peel after peeling approximately 0.1 in. Values reported are maximum
stresses immediately before catastrophic failures.
mSeam fabricated by supplier.
"Specimens failed in bond between adhesive and liner surface.
°Specimens ripped uncontrollably once peel was initiated. Value reported is maximum stress.
POne specimen failed at jaw bite; the other failed catastophically at the line of pee! after peeling approximately 0.1 in.
9Specimens failed at jaw bite.
rSpecimens initially failed at the bond between the two liner surfaces, then failed by ripping uncontrollably.
S0ne specimen failed at the bond between the two liner surfaces; the other initially failed at the bond between the two surfaces, then ripped uncontrollably.
-------
Because of the high thread count, 22 x 11 epi, the unexposed butyl
rubber sheeting broke with the fabric at 60% elongation in the machine
direction and at 25% in the transverse direction; thus retention values
could not be calculated for stress at 100% elongation (S-100).
This sheeting had a volatiles content (predominantly moisture) that
was particularly high after exposure to the acidic waste and modest after
exposure to the pesticide waste, probably reflecting the high inorganics
content of the butyl compound (Table 38). The extractables as shown in
Table 39 did not change appreciably, indicating that the compounding oil
was retained during the exposure to the wastes. Exposure to an oily waste
would probably have resulted in a significant increase in extractables.
The sheeting appeared to have softened considerably in the acidic waste and
developed a high elongation as shown in Table 40. In the other wastes the
elongation increased. The softening of the butyl did not appear to
affect the nylon scrim.
The 2-in. seam of the butyl rubber specimen was made with a two-part
vulcanizable adhesive furnished by the supplier. The unexposed seam failed
in the shear mode in the clamp indicating the seam strength was greater
than 84.8 ppi. The exposed samples failed predominantly at the clamps also
and test values were somewhat less, possibly indicating a loss in the
strength of the nylon fabric.
In the peel mode, the original adhesion was 8 ppi with the failure
in the adhesive, but the exposed samples delaminated at values of 3.6 to
5.3 ppi. This type of failure indicates loss in ply adhesion during
exposure to the wastes.
Overall, except for peel adhesion, the butyl rubber specimens showed
good retention of their original properties on exposure to the four wastes.
The effect of time was not large. The waste which caused the greatest
change, perhaps, was the acidic waste in which the butyl increased in
volatiles content significantly. It should be recognized that this liner
was not exposed to an obviously oily waste, which would have caused soften-
ing and loss of tensile.
Chlorinated Polyethylene (CPE) Membrane--
The CPE (No.77) was a thermoplastic sheeting of 30 mil nominal thick-
ness and was not fabric-reinforced. It had an original ash content of
12.56% and an extractables content of 9.13%. The volatiles of the unex-
posed material was 0.14%. Two sets of specimens of this sheeting were
exposed to five wastes:
Acidic waste, "HN03-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Oily waste, "Oil Pond 104"
Pesticide waste.
123
-------
The first set of specimens was removed from exposure after 450 to 526
days and the second set after 1218 to 1358 days.
The CPE membrane showed significant increases in volatiles content in
the acidic, lead, and pesticide wastes, probably reflecting the absorption
of water. The increase during exposure to "Oil Pond 104" waste was prob-
ably due to absorption of oil as well as of water. The smallest increase
in volatiles was in the specimen exposed to the spent caustic. The modulus
in all cases showed an initial drop and then an increase, indicating
initial swelling followed by crosslinking. However, there were losses in
modulus in the lead waste and in the oily waste. The only significant
increase in the extractables during exposure was in the CPE liner exposed
to the oily waste, "Oil Pond 104."
The 2-in. seams of the CPE specimens were prepared by Matrecon using a
solvent weld that was a 1:1 mixture of toluene and tetrahydrofuran (THF).
The unexposed seam had a strength in shear of 48.3 ppi, and failed at the
seam edge. The exposed samples generally had lower adhesion, reflecting
the loss in strength of the CPE liner during exposure. The failures were
at both the seam edge and in the clamp area. Again, the oily wastes appear
to reduce the values, which is a reflection of the loss in the strength of
the sheeting.
The unexposed seam had a strength in the peel mode of 21.4 ppi with
failure at the bond between the two liner surfaces. On exposure, most
of the failures were between the two liner surfaces, although one of the
exposed specimens in the "Oil Pond 104" waste and one in the "Spent
caustic" waste failed catastrophically at the peel line during the test.
It appears that the oily waste affected somewhat the strength of the
seam.
Overall, in this exposure test, the CPE membrane appeared to be
satisfactory for the inorganic aqueous solutions but showed significant
losses in properties in contact with oily wastes.
Chlorosulfonated Polyethylene (CSPE) Membrane--
The CSPE membrane (No. 6R) was a fabric-reinforced nylon with a thread
count of 8 x 8 epi and a thickness of 34 mils. The CSPE compound contained
3.28% ash, had an extractables content of 3.77%, and a volatiles content of
0.51%. Two sets of specimens of this polymeric membrane were exposed to
five wastes:
Acidic waste, "HN03-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Oily waste, "Oil Pond 104"
Pesticide waste.
The first set of specimens was removed after 499 to 526 days of exposure
and the second set after 1218 to 1357 days of exposure.
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On exposure all the CSPE membrane specimens increased significantly in
volatile contents (Table 38) in all the wastes. Though volatiles of the
CSPE liner increased in the spent caustic and pesticide wastes, the magni-
tude appeared to be leveling off at the time the second set was removed.
The extractable (Table 39) changed only modestly during the exposure. The
highest extractable content measured after exposure was for the liner that
had been exposed to "Oil Pond 104" waste; in this case, the extractables
increased from 3.77 to 9.45%. The elongation at break of the sheeting
decreased with exposure time in all cases, indicating that crosslinking was
taking place. This is confirmed by the increases in the S-100.
The seam of the CSPE membrane was prepared by Matrecon using a bodied
solvent adhesive furnished by the supplier. The unexposed 2-in. seam had a
strength in shear of 62.1 ppi with failure at the seam edge. After expo-
sure, the shear values were generally somehwat lower with the locus of
failures varying from the seam edge to the edge of the clamps with some
failing in the sheeting itself. The greatest drop in seam strength values
was with the seams exposed to the acidic waste; these drops probably
reflect the loss in strength of the nylon fabric.
The strength of the unexposed seam in the peel mode was 23.2 ppi; one
specimen failed by del ami nation and the other failed in the adhesive.
After exposure, there was little or no loss in the strength of the mem-
branes exposed in the "Spent caustic" and the lead waste although failures
were partially by del ami nation; the principal loss in strength of the test
specimens were in those exposed to the acidic waste, "Oil Pond 104" waste,
and the pesticide waste. The failures were predominantly a combination of
delamination and failure of the adhesive. These failures indicate that the
loss in ply adhesion may be causing the loss in seam strength.
The results of the exposure of the CSPE membrane to the five wastes
indicate that this CSPE sheeting tends to absorb water and wastes and some
oil when exposed to wastes containing oily constituents. The effect of
aging and exposure to wastes showed a modulus increase and decreases in
elongation.
Another CSPE membrane was tested in a primary exposure cell where it
was used to line immersion tanks containing deionized water and a 50:50
blend of deionized water and water from "Well 118." (Data are reported in
Appendix I). This sheeting had a nominal thickness of 30 mils and was
reinforced with 8x8 epi polyester scrim.
Note: A new grade of CSPE compound was introduced during the
time this project was underway but was not included in any
of the tests reported. This new barrier compound is
significantly more resistant to swelling by different
liquids. Also, there has been a shift from nylon to
polyester as the reinforcing fabric (Matrecon, 1983).
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Elasticized Polyolefin (ELPO) Membrane--
The elasticized polyolefin membrane (No. 36) was a black thermoplastic
sheeting based on polyethylene. It contained a small amount of crystal -
Unity and had a thickness of 22 mils, a specific gravity of 0.938, an ash
content of 0.9%, a volatiles content of 0.15%, and an extractables content
of 5.5%. During the course of the project, this sheeting was exposed as a
primary liner to 12 different wastes or test media which included:
Acidic wastes:
"HFL"
"HN03-HF-HOAc"
Alkaline wastes:
"Slop water"
"Spent caustic"
Lead waste
Oily wastes:
"Oil Pond 104"
"Slurry oil"
"Weed oil"
Pesticide waste
Well water, "Well 118"
"Well 118":water, 50:50
Deionized water.
The initial exposures were tested in duplicate with the following wastes:
Acidic waste, "HNOs-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Oily wastes:
"Oil Pond 104"
"Slurry oil"
Pesticide waste.
Subsequently, in order to furnish tanks for immersion testing, the remain-
ing wastes were placed into exposure testing in combination with the ELPO
liner. Some results of exposure to these wastes are reported in Tables 37
through 44.
126
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The elasticized polyolefin liner had only small increases in volatiles
content in those wastes that were predominantly water; for example, the
pesticide, the lead, and the "Spent caustic" wastes. Exposure to those
wastes that contained oily constituents, particularly with the "Oil Pond
104" waste and the "Slurry oil" waste, resulted in increased volatiles
contents. There were significant increases in the extractables content of
the elasticized polyolefin by the oily wastes which resulted in major drops
in tensile strength and modulus and softening of the sheeting. There was
also a significant increase in volatiles content by the elasticized poly-
olefin exposed to the acidic waste, "HN03-HF-HOAc" i.e. 5.3% in 1217 days
and to the alkaline waste, i.e. 10.83% in 2299 days.
The seam in the elasticized polyolefin specimen was 0.5 in. in width
and was made by the supplier using a heat sealing device of their design.
This method of seaming was used in both factory and field. The value of
original strength of the seam tested in the shear mode was 28.8 ppi with
the failure at the seam edge. Almost all of the values measured after
exposure were higher and all were at the seam edge. The only measurements
that came in lower were taken from the specimens that had been exposed to
"Oil Pond 104" waste; their strengths in shear were 19.3 and 18.3 ppi at
521 and 1357 days, respectively, reflecting the loss in the strength of the
sheeting.
In the peel mode the value was 21 ppi with failure at the line of
peel, which occurred catastrophically. The values of most of the exposed
specimens were the same as was the type of failure. The specimens exposed
to "Oil Pond 104" waste and the "Slurry oil" waste were lower, probably
reflecting the loss of strength of the sheeting resulting from absorption
of the oil from the wastes.
Overall, the elasticized polyolefin lining material showed good
retention of properties in the aqueous wastes. However, those wastes that
contained significant amounts of oil were absorbed by the liner, resulting
in loss of tensile strength, modulus, and tear strength. Problems with the
ELPO seams are indicated by the types of failure when tested in peel.
Note: The adverse effects of oil on this sheeting were also
observed in the tub test described in Section 8.
Ethyl ene Propylene (EPDM) Membrane
The EPDM rubber (No. 26) that was tested was a crosslinked sheeting of
30-mil thickness. It had a specific gravity of 1.169, an ash content of
7.67%, a volatiles content of 0.50%, and an extractables content of 22.96%.
The high extractables content shows the high oil content that is common to
many EPDM compounds. Two sets of specimens of this sheeting were exposed
to four different wastes:
Acidic waste,"HN03-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Pesticide waste.
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The oily wastes were specifically excluded from the exposure testing based
upon the preliminary compatibility testing and the oil sensitivity of this
type of rubber.
The first set of test specimens was removed after 497 to 526 days of
exposure and the second set after 1147 to 1344 days of exposure.
This sheeting increased in volatiles content in all the wastes, par-
ticularly on exposure to acidic waste; these volatiles were predominantly
water. The extractables changed slightly, generally upward.
The 2-in. seam incorporated in the EPDM exposure specimen was fabri-
cated by Matrecon using a two-part vulcanizable adhesive and a gum tape
furnished by the supplier. The seam had a strength in the shear mode of
39 ppi with the failure in the adhesive. After exposure, the values in the
shear mode were all higher except for the seam in the sample that was in
contact with the lead waste, for which there was a substantial loss in
value. In all except one case, the failures were in the adhesive.
In the peel mode, the adhesion was 4.9 ppi which, as in the case of
the shear mode, was retained during exposure, except for the lead waste.
After 499 days of exposure the adhesion was 3.5 ppi and after 1344 days it
was 2.3 ppi.
Overall, the EPDM membrane was affected only moderately by the four
wastes to which it was exposed. Of the four wastes, the acidic waste
appears to have been the most aggressive toward the EPDM compound; the
effects, however, were not large. The seam strength was low before expo-
sure and decreased with exposure, indicating a probable inadequacy of the
seaming method. This membrane was not exposed to oily wastes which would
have severely swelled it.
Neoprene Membrane--
The neoprene sheeting (No. 43) that was tested was vulcanized and not
fabric-reinforced. It had a nominal thickness of 34 mil, a specific gravity
of 1.477, an ash content of 12.3%, a volatiles content of 0.45%, and an
extractables content of 13.69%. Two sets of specimens of this membrane were
exposed initially to four different wastes:
Alkaline waste, "Spent caustic"
Lead waste
Oily waste, "Oil Pond 104"
Pesticide waste.
Subsequently, it was exposed to two additional wastes in exposure
tanks for the immersion testing:
Industrial waste, "Basin F"
Well water waste, "Well 118"
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Because neoprene is generally considered to be an oil-resistant rubber,
it was exposed to the oily wastes, as wastes of this type are aggressive to
many of the lining materials.
The first set of specimens was removed from exposure after 494 to 526
days and the second set was removed after 1237 to 1356 days.
All the neoprene membrane specimens increased substantially in vol-
atiles content in all of the wastes, increasing from 0.45% to 11.29 -
21.31%, except in the "Spent caustic," in which the values increased 4.40
to 5.67%. On the other hand, the extractables content changed little even
for the specimens exposed to the oily wastes. Consequently, it appears
that most of the liquid absorbed by the neoprene specimens was water. The
neoprene specimens exposed to the lead waste, "Oil Pond 104" waste, and the
pesticide waste softened considerably and had a low retention of S-100.
This is probably the result of absorbing water. The specimens exposed to
the spent caustic softened little and retained their elongation best,
probably the result of the high dissolved solids content of the wastes.
Low absorption of highly concentrated brines is characteristic of neoprene
compounds.
The 2-in. seam incorporated in the neoprene specimen was fabricated by
Matrecon with a lap sealant furnished by the supplier. The strength of the
unexposed seam in the shear mode was 45.7 ppi with the failure at the bond
between the adhesive and the liner surface. The effects of the exposures
to the different wastes varied with the waste. In the case of the seams
exposed to "Spent caustic" waste the test value for seam strength increased
with the failures occurring at the clamp edge or in the sheeting. In the
case of the lead waste, the strength value was less with failures both at
the surface of the adhesive and in the liner itself. For the seam in the
liner exposed to "Oil Pond 104" waste, some of the failure was in the
adhesive but the principal failure was in the sheeting, reflecting the loss
in strength due to the absorption of the waste. In the case of the seams
in the specimens exposed to the pesticide waste, the failures of the test
specimens were at the clamp edge or at the seam edge. The low values
probably reflect the loss of strength of the sheeting.
In the peel mode, the unexposed seam had a strength of 8.2 ppi with
failure at the bond between the adhesive and the liner. The failures in
all of the exposed specimens were of this type; however, the peel strength
of the seams increased during the exposure in the spent caustic, but
decreased during the exposure in the oily and lead wastes.
The neoprene membrane (No. 43) showed considerable absorption of
both water and oily constituents. The water absorption was the lowest on
exposure to the "Spent caustic" waste, which is essentially a concentrated
brine, a type of medium in which neoprene compounds are known to have low
absorption. The effect on physical properties also varied considerably
depending largely on the amount of swelling, which is indicated by the
volatiles. The oil resistance normally associated with neoprene was not
apparent in these tests. It appears that, if a neoprene membrane is being
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considered for lining a water impoundment, it should tested for compati-
bility with a sample of the waste to be impounded or a prototype of that
waste.
Polyester Elastomer (PEL) Membrane--
The polyester elastomer membrane (No. 75) was a developmental product
with a thickness of 7 mils. It was furnished by the supplier with a
heat-sealed seam, because a higher temperature than we could obtain with
our equipment was needed to prepare seams. This film was based on a
partially crystalline polymer that melts in the 188 to 207°C range. It had
a specific gravity of 1.236, a volatiles content of 0.26%, an extractables
content of 2.74%, and an ash content of 0.38%. A thermogravimetric anal-
ysis of this film indicated that it contained 91% polymer, 3% plasticizer,
and 6% carbon black.
The polyester elastomer sheeting was included in this project because
of its reported resistance to hydrocarbons and other oily materials. As a
primary liner it was exposed to six wastes:
Acidic waste,"HN03-HF-HOAc"
Alkaline waste, "Spent caustic"
Lead waste
Oily wastes:
"Oil Pond 104"
"Slurry Oil"
Pesticide waste.
The first set of samples was removed from exposure after 328 to 526
days and the second set was removed after 509 to 1357 days.
This was the only material in the entire program that failed by
cracking and leaking on exposure to a waste, in this case, the acidic waste
"HN03-HF-HOAc". This shows the sensitivity of this polymer to acidic
materials which caused it to degrade by hydrolysis. After 323 days of
exposure to this waste, it had retained only 33% of its tensile strength
and lost almost all of its elongation.
With respect to exposure in the oily wastes, the polyester elastomer
lost significantly in its physical properties in the "Slurry oil" waste and
similarly, but not to the same degree, in the "Oil Pond 104" waste. This
lining material had its best retentions in the pesticide and the "Spent
caustic wastes.
The 0.5-in. wide seam incorporated in the polyester elastomer sheeting
was furnished by the supplier and was made by heat sealing. The strength
of the unexposed seam in the shear mode was 21.2 ppi with the failure
occurring at the seam edge. The strength of the seams after exposure
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remained high. The test specimens broke either at the seam edge or at the
clamp edge. There was some indication that the lower values where the
failures occurred at the clamp edge were the result of the somewhat lower
strength of the sheeting due to absorptions of oily constituents from the
wastes.
The strength of the unexposed seam in peel was 20.8 ppi with failure
occurring at the line of peel. On exposure to the lead, oily, and pesti-
cide wastes, there was some reduction in strength with the breaks predomi-
nantly at the peel line.
The results show that PEL membranes should not be exposed to highly
acidic wastes, but indicate that they may be useful for specific waste
streams. Compatibility tests must be carried out with a sample of the
waste to be contained or with a prototype of that waste.
Note: The polyester elastomer sheeting was the thinnest of all
the materials tested in this project. New versions of
this type of material are now available with improved
properties for liner applications.
Polyvinyl Chloride (PVC) Membrane --
The specific polyvinyl liner membrane (No. 59) that was tested was a
sheeting with a nominal thickness of 30 mils. It had a specific gravity of
1.280, an ash content of 6.97%, a volatiles content of 0.3%, and an ex-
tractables content of 35.86%. The high extractables, largely plasticizer,
is equivalent to about 60 parts per 100 g of PVC resin. Specimens of this
membrane were placed in exposure with 8 different wastes:
Acidic wastes:
"HFL"
"HNOs-HF-HOAc"
Alkaline wastes:
"Slop water"
"Spent caustic"
Lead waste
Oily wastes:
"Oil Pond 104"
"Slurry oil"
Pesticide waste.
The first set of exposures were tested in duplicate with the following
wastes:
Acidic waste:
"HN03-HF-HOAc"
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Alkaline waste:
"Spent caustic"
Lead waste
Oily waste:
"Oil Pond 104"
Pesticide waste.
Subsequently, in order to furnish tanks for immersion testing, the
following wastes were placed in the exposure test in combination with the
PVC membrane:
Acidic waste:
"HFL"
Alkaline waste:
"Slop water"
Oily waste:
"Slurry oil"
The exposures varied from 327 days to 1565 days.
The effects of exposure varied with the different wastes. The
volatiles increased for all of the exposed specimens except for the speci-
men that was in contact with the "Slurry oil" waste. In most cases, the
amount did not increase greatly after the initial exposure time. However,
the increase was substantially greater for the specimens exposed to "Slop
water" and the strong acid, "HN03-HF-HOAc." The extractables of the
exposed specimen varied considerably; all, however, tended to be lower than
the original value, indicating loss of plasticizer. The specimen exposed
to the "Slop water" had the lowest extractables content, indicating
a major loss of plasticizer. The specimens in the acidic waste also
had a significant loss, although not as large as the specimens exposed to
the "Slop water." Specimens in the "Spent caustic" and the pesticide
wastes changed little. However, the extractables content of the specimens
exposed to the lead waste and to "Oil Pond 104" waste dropped during
exposure, indicating some loss of the plasticizer to the oily wastes. The
effect upon physical properties was more severe. The specimens that had
been exposed to the "Slop water" lost almost all of their elongation and
became very hard. The specimen that had been in contact with the acidic
waste, "HN03-HF-HOAc," lost in elongation and more than doubled in modu-
lus S-100. Also, the specimens exposed to "Oil Pond 104" waste and the
weaker acidic waste, "HFL," increased in modulus.
The 2-in. seam incorporated in the PVC specimens was fabricated by
Matrecon by solvent welding using a solvent consisting of two parts or
tetrahydrofuran and one part of cyclohexanone. The strength of the seam in
shear was greater than 69 ppi with the failure occurring at the clamp edge.
On exposure the failures were predominantly in the seam edges although some
132
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occurred outside the seam, hut not at the clamp. The values on exposure
were erratic; some values fell to 45 ppi and others rose to 77 ppi, more or
less reflecting the strength of the sheeting itself. No failures occurred
within the seams.
In the peel mode the original value for the unexposed seam was 15.2
ppi, with the bond failure between the liner surfaces. Again, on exposure,
the results varied considerably, ranging from 9.8 ppi to 34 ppi. In almost
all cases, the peel strength of the seams increased.
Exposure to the alkaline "Slop water" waste resulted in a major
loss of plasticizer and a large increase in the volatiles content which
resulted in a major stiffening and embrittlement of the liner. The elonga-
tion dropped to 3% of the original value after 1565 days of exposure and
the extractables dropped to 10.4%. The second alkaline waste, "Spent
caustic", did not have such an adverse effect. Exposure to the acidic
wastes caused hardening of the materials and some loss in elongation, but,
even after 1565 days, the effects were not large. The effects of the
exposures to the oily wastes varied with the individual waste. The "Slurry
oil" waste affected the sheeting only modestly during 327 days of exposure.
However, the membrane exposed to "Oil Pond 104" waste showed increases in
modulus, reduction in elongation, and some hardening; in the latter oily
waste the extractables content was reduced, indicating that some of the
plasticizer was lost during exposure.
The PVC membrane showed considerable variation in its response to
the different wastes to which it was exposed. The variation was largely
related to the amount of swell and the loss of plasticizer that took place
during the exposure. This indicates the necessity of performing compati-
bility tests of the PVC membrane being considered with the waste it would
impound.
An additional PVC sheeting (No. 92) was tested in the primary exposure
cells where it was used to line two cells that served as immersion tanks.
These cells contained deionized water and a 50:50 blend of deionized water
and wellwater from "Well 118." This PVC sheeting was unreinforced and had
a nominal thickness of 20 mils. (Data are presented in Appendix I). The
effects of the exposure for approximately 980 days in both media were
modest. This membrane softened after somewhat in DI water but hardened
somewhat in the 50:50 "Well 118":DI water blend.
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SECTION 7
IMMERSION TESTING OF POLYMERIC MEMBRANE LINERS
Only a limited number of combinations of polymeric membranes and
wastes could be included in the primary exposure testing program. However,
many other polymeric membranes were available and other potential lining
materials were becoming available. These materials included membranes
based on new polymers and on the polymers selected for the primary exposure
program but of significantly different composition. It was desirable to
expand the scope of the project to include a wider range of polymeric
membranes in the waste liquids available. Furthermore, one of the objec-
tives of this project was to develop testing procedures which could be
used to assess lining materials, particularly for compatibility with waste
streams.
In rubber and plastics technology, the compatibility of polymeric
products being considered for service with a solvent or liquid is commonly
tested by immersing samples of the rubber or plastic compound in that sol-
vent or liquid. In this type of testing the changes in weight, dimensions,
and physical properties can be used to monitor the effects of immersion.
It is, of course, desirable that no changes in the material occur during
service; therefore, changes in dimensions and in properties can indicate a
degree of incompatibility. In some applications, specific changes in
properties of the material limit the serviceability of a product. For
example, a fluid delivered by a rubber hose may cause excessive shrinkage
which could stiffen the hose, or swelling which could restrict the flow in
the hose to such an extent that the hose would no longer be serviceable.
Waste liquids can cause changes in the dimensions as well as changes in the
physical properties of polymeric lining materials; therefore, measuring
changes in dimensions and physical properties should be satisfactory for
measuring the compatibility of polymeric lining materials.
In the initial selection of combinations of liners and wastes for
long-term exposure testing, the combinations were screened by immersing
small strips of the liners in the different wastes. It was felt that
short-term tests of a few weeks or less would indicate those combinations
which were incompatible and should not be included in long-term exposure.
This testing quickly eliminated several combinations; however, longer term
tests were needed to reflect the effects of extended exposure. Prolonged
immersion tests had been run in assessing liners for municipal solid waste
liners (Haxo et al, 1982). The results of these immersion tests correlated
well with the effects of exposure in the municipal landfill simulators.
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The combinations of wastes and liners selected for immersion testing
in this project included combinations already being tested in the primary
cells plus combinations of additional liners and wastes that had become
available. Including some of the same combinations in both the immersion
and the primary exposure was desirable for developing a correlation bet-
ween the two-sided exposure in immersion testing and the single-sided
exposure that took place in the primary cells.
The procedure followed for the immersion tests in this project is
described in the following subsection.
DESCRIPTION OF METHOD OF IMMERSION TESTING
Although the exact method that was followed in immersion testing
changed somewhat during the course of this project, the basic procedure was
as follows:
The exposure specimens, approximately 8 x 6 in., were totally
immersed in the tanks of the primary cells, which held about
8 gal of waste, for two time periods, the longer period ranging
up to several years. These slabs were preweighed and their
dimensions measured. The slabs were then hung in the waste
fluids with either stainless steel wire or polypropylene cord.
A sufficiently large sample was selected so that physical test
specimens could be cut in both the machine and transverse
directions, as discussed below. The grain of the first set of
specimens that was immersed was across the width; that is, the
machine direction ran in the short dimension of the specimens.
In later testing the grain was oriented in the lengthwise direc-
tion in which the specimens were hung.
Since the test was primarily concerned with the durability and per-
formance of the barrier component of the liner, unreinforced (no fabric)
materials were generally selected for this program. Nevertheless, two
fabric-reinforced materials were included because the barrier compositions
were not available without fabric at the time the project started; one of
the two was a lining material included in the primary exposure. Two
specimens of each lining material were immersed in each waste so that
exposure data could be obtained for two time periods.
TESTING OF IMMERSED SLABS
The initial tests of the materials to be immersed were performed in
accordance with ASTM test methods, i.e. the full number of replications
with full-size test specimens were included in all of the tests. Results
of these tests are reported in Appendixes F and G. However, in measuring
the properties of the materials after immersion, a reduced number of
specimens were tested for some properties and, in the case of the tensile
testing, a special die with tab ends smaller than called for by ASTM D412
and D638 was used in preparing the test specimens (Figure 21). The reduced
specimen size allowed us to optimize the amount of testing that could be
performed on the immersed slabs. The testing that was performed toward the
135
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end of the project is listed in Table 45. In the early part of the project
all the liners, even those that were fabric-reinforced or crystalline, were
tested as if they were crosslinked rubbers or thermoplastics. Later, the
crystalline and the fabric-reinforced materials were tested as shown in
Table 45.
Measurements on Immersed Specimens
Before immersion the following measurements were made on each slab:
- Thickness.
- Dimensions in both machine and transverse directions.
- Weight.
During immersion all of these properties changed to varying amounts. If
the liner materials absorbed waste constituents, generally all the values
for the above parameters increased.
Due to the effect of the grain introduced into the materials during
manufacture, change of dimensions differ between the machine and transverse
directions. In some cases, shrinkage would occur in machine direction and
swelling in the transverse direction.
t
1
wo
v^,
^
\
w
t
i n
X"
\
Figure 21. Special dumbbell for tensile testing of polymeric membrane
specimens after immersion in waste liquids or test media.
The dimensions are:
W - Width of narrow section 0.25 in.
L - Length of narrow section 1.25 in.
WO - Width overall 0.625 in.
LO - Length overall 3.50 in.
G - Gage length 1.00 in.
D - Distance between grips 2.00 in.
The width, W, of this specimen is the same (0.25 in.) as that
of the Die C dumbbell in ASTM D412 and Type IV of ASTM D638.
The dimension, L, in the latter dumbbell is 1.30 in. in com-
parison with the 1.25 in. of this dumbbell.
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TABLE 45. TESTING OF POLYMERIC MEMBRANES IN THE IMMERSION TEST
Type of compound and construction
Test
CO
CrossJmked or vulcanized
Thermoplastic
Crystall me
Fabn c-rei nf orced
Measurements on imnersed
specimens
Thickness, method
Report
Dimensions, method
Report
Weight, method
Report
Analytical properties
Volatiles - method
Report
Extractables - method
Report
Physical properties
Tensile properties
Method
Type of specimen
Number of specimens
Speed of test
Values to be reported
Dead weight gage, mils
Percent change
Ruler graduated to 0.01-in.
Percent change in machine
and transverse directions
Analytical balance
Percent change
MTM-la
Moisture, %
Non moisture, %
MTM-2b
Solvent
ASTM D412
Special dumbbell0
3 in each direction
20 ipm
Tensile strength, psi
Elongation at break, 1
Stress at 100 and 200%
elongation, psi
ASTM 0638
Special dumbbell0
20 ipm
Tensile strength, psi
Elongation at break, %
Stress at 100 and 200%
elongation, psi
ASTM D638
Special dumbbell0
2 ipm
Tensile stress at yield, psi
Elongation at yield, I
Tensile strength at break, psi
Elongation at break, %
Stress at 100 and 200% elong-
ation, psi
ASTM D751, Mtd B
1-in. wide strip and 2-in.
"jaw" separation
12 ipm
Tensile at fabric break, ppi
Elongation at fabric break, %
Tensile at ultimate break, ppi
Elongation at ultimate break, %
Stress at 100 and 200% elong-
ation, ppi
Modulus of elasticity
Method
Type of specimen
Speed of test
Strain rate
Tear resistance
Method
Type of specimen
Number of specimens
Speed of test
Puncture resistance
Method
Type of specimen
Speed of test
Number of specimens
Report
Hardness, Duro (5-sec)
ASTM D882
Strip 0.5 x 6-in.
0.2 ipm
... ... 0 .1-1 n ./i n ./mi n . ...
ASTM D624 ASTM D1004 ASTM D1004 d
Die C
2 in each direction > >
20 ipm 20 ipm 2 ipm
FTMS 101B-2065 > >
2 x 2-1 n. > >
20 ipm > >
1 or 2 > >
Thickness, mil > >
Stress, Ib > >
Elongation, in. > >
Duro A > Duro D Duro A
Duro D (if Duro A >80) Duro D (if Duro A >80)
aMatrecon Test Method No. 1 (Matrecon, 1983, pp. 338-39).
DMatrecon Test Method No. 2 (Matrecon, 1983, pp. 340-43).
cSee Figure 21.
dNo tear resistance test is recommended for fabric-reinforced sheetings in the immersion study.
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Analytical Properties
In addition to the weight change that occurred in the test specimens,
the volatiles and the extractables of the specimens were determined. Both
of these properties relate to the amount of waste that is absorbed by or
the components that are extracted from a liner material. Most of the
volatiles are moisture, and the difference between the moisture component
and the nonmoisture component was not distinguished during most of the
testing.
The extractable content of a polymeric membrane can change during
immersion by the absorption of nonvolatile organic constituents into the
lining material and also by the extraction of parts of the original com-
pound, e.g. plasticizers, by the waste fluid.
Physical Properties
The following physical properties of the membranes were measured after
two different periods of immersion:
- Tensile properties, including tensile strength, elongation at
break, and stresses at 100 and 200% elongation.
- Modulus of elasticity for crystalline type materials.
- Tear resistance for all materials except the fabric reinforced.
- Puncture resistance.
- Hardness.
The tear resistance of the fabric-reinforced membranes was not deter-
mined because the fabric in the Type C test specimens does not break but
pulls out of the rubber matrix during the test. In order to get threads to
break during tear testing, considerably larger specimens are required than
the ASTM D624 Die C type test specimen. Specimens 8 x 6 in. are used to
measure tear resistance of fabric-reinforced membranes.
Puncture resistance measured in accordance with Federal Test Method
Standard 101B-2065 was particularly convenient for determining the effect
of immersion. If there was sufficient material, this test was run in
duplicate.
Hardness changes reflected the softening or hardening of the material
during immersion. Durometer A was measured on all except the crystalline
type materials and Durometer D was used in addition to Durometer A if the
Durometer A reading was greater than 80 points.
The anisot ropy introduced in the liner material by the grain affects
the tensile and tear properties of the sheeting and, consequently, these
were run in both directions as discussed in the results in this section.
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SPECIFIC COMBINATIONS OF MATERIALS AND LIQUIDS
PLACED IN IMMERSION TESTS
The immersion testing performed in this program was done in five
groups:
- Group I consisted of 12 different polymeric membrane liners
immersed in 9 different wastes. Five of the membranes were
the same as those tested as liners for primary cells.
- Group II consisted of the testing of the same lining materials
immersed in two important standard test media, i.e. distilled
water and a 5% solution of NaCl.
- Group III added a cross linked CPE and three crystalline materi-
als to the program. These materials were tested in the wastes
and two standard test media already in the test and an indus-
trial waste that contained considerable heavy metals and some
organics.
- Group IV consisted of all the initial 12 liners in immersion
in the industrial waste.
- Group V consisted of the 16 polymeric lining materials in a
saturated aqueous solution of tributyl phosphate.
These groups are shown in the matrix given in Figure 22 and their selection
is discussed in the following subsections.
First Group of Immersion Tests
In order to extend the scope of testing to other membranes and wastes
and to develop correlation between immersion-type testing and the testing
in the primary cells, 5 of the original lining materials, i.e. CPE (No.
77), CSPE (No. 6R), elasticized polyolefin (No. 36), polyester elastomer
(No. 75), and PVC (No. 59), were placed in immersion in all of the wastes
that were in the primary test and some additional wastes, i.e. a second
acidic waste "HFL" (W-10), a second alkaline waste, "Slop water" (W-4), and
a third oily waste, "Weed oil" (W-7). Seven additional polymeric membranes
also were included.
The butyl rubber liner (No. 44) was added. Even though its 62.5-mil
thickness was greater than desired, this lining material was selected
because it was not fabric-reinforced. The high thread count (22 x 11 epi)
of the fabric in the butyl rubber sheeting in the primary exposure testing
program caused problems in evaluating the butyl itself and it was felt that
a butyl material without fabric, even with its greater thickness, would be
better for such evaluation.
A second CSPE (No. 55) was added. In contrast to the first CSPE liner
(No. 6R), it did not have fabric reinforcement. However, as was the case
with the first CSPE, it was based upon a "potable" grade CSPE compound.
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WASTE LIQUID
POLYMERIC LINER
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Chlorosulfonated
polyethylene
Elasticized
polyolefm
Ethylene propylene
rubber
Ethylene propylene
rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Chlorinated
polyethylene
Polyethylene
High density
Low density
Polypropylene
ACIDIC
ALKALINE
Saturated
Basin solution
F of TBP
(W-16) (W-20)
A primary membrane
Figure 22. Groups of polymeric membrane liners placed in immersion in different wastes,
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Both lining materials were produced by the same manufacturer and were
approximately the same composition.
Note: "Industrial" or low water absorption grade CSPE was not
available at the time the immersion was begun.
Two EPDM membranes were added; one was a thermoplastic, fabric-rein-
forced sheeting (No. 83R with polyester). This was the first thermoplastic
EPDM compound that we received. The second EPDM membrane was vulcanized
and was 36 mils in thickness. It served as a replicate for the EPDM
membrane that was being tested in the primary cells.
A neoprene (No. 90) membrane was placed in the immersion test. It
had approximately the same thickness as the liner in the primary test;
however, the compound differed in composition.
Two additional PVC membranes were added because of the large usage of
PVC membranes as lining materials. One of the PVC's had a thickness of
30 mils and the second had a thickness of 20 mils.
Second Group of Immersion Tests
Two media that are often used in the testing of materials are de-
ionized water and aqueous salt solutions of known concentrations, e.g. a
5% NaCl solution. Such liquids can be points of reference for many wastes.
Deionized water could potentially be used in compatibility testing as a
base point though in some instances deionized water can affect a polymer
composition, e.g. some chlorinated polymers, more adversely than do aqueous
solutions containing dissolved inorganic salts. A brine solution is of
interest because of the number of wastes which contain salt. A 5% brine
solution was selected as a test fluid.
All of the 12 membranes that were part of the first group were in-
corporated in this second group of immersion tests.
Third Group of Immersion Tests
The third group of liners and wastes consisted of a vulcanized CPE
membrane (No. 100) and three partially crystalline materials, HOPE (No.
105), LDPE (No. 108), and polypropylene (No. 106) immersed in all of the
13 wastes.
The crosslinked CPE was a developmental material which was of interest
because its crosslinking should make it more resistant to swelling in
liquids. The three partially crystalline materials were added because of
the favorable performance that crystalline materials, such as the ELPO and
the polyester, had shown both in this project and in the municipal solid
waste project (Haxo et al, 1983) in which LDPE and polybutylene had been
studied.
Samples of these materials were obtained in 30-mil thickness from a
local plastics supply firm in order to match the thickness of many of the
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liner materials under test. None of the three sheetings were commercial
lining materials and none of them contained carbon black. At the time this
facet of the work was undertaken (1977) only thin membranes (5-10 mils) of
low density polyethylene were available and had been used in lining appli-
cations. Also, there was an indication that membrane liners of polypro-
pylene had been used and that membrane liners of high-density polyethylene
would become commercially available in the near future. Testing of the
HOPE membrane liners that subsequently became available showed that the
HOPE used in this project was considerably different in several respects
from the HOPE now used in commercial linings.
These additional four membranes were immersed in the available wastes
which were used for testing the first two groups of immersion tests and
in an additional industrial waste that had become available and which was
considerably different from the wastes that had been undergoing test. This
waste ("Basin F," W-16) contained high levels of heavy metal constituents
and some organics.
Fourth Group of Immersion Tests
The 12 lining materials included in the first two groups of immersion
tests were placed in immersion with the industrial waste "Basin F" (W-16)
in the fourth group of immersion tests. Because only one cell containing
Basin F was available for the immersion, only one set of specimens of each
of the 12 materials were immersed.
Fifth Group of Immersion Tests
The fifth group of immersion tests consisted of all 16 of the lining
materials placed in a dilute but saturated solution of an organic chemical
in water. The objective of this test was to assess the effects of a
small concentration of a known organic in a water solution. The purpose
for this group of exposures is discussed more fully below in the section
entitled, "Immersion of Membranes in Saturated Aqueous Solutions of Tri-
butyl Phosphate." The tributyl phosphate was selected because of its
solubility in water and its relative nonvolatility. Under special cir-
cumstances it had been used as a plasticizer for PVC.
RESULTS OF IMMERSION TESTS
The results of the immersion tests are presented in a series of seven
tables in Appendix J, "Exposure of Liner Specimens in Immersion Tests":
J-l. Number of Days of Immersion.
J-2. Dimensional Changes in Machine and Transverse Directions.
J-3. Percent Increase in Weight.
J-4. Percent Volatiles After Immersion.
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J-5. Percent Extractables After Immersion.
J-6. Retention of Stress at 100% Elongation.
J-7. Retention of Elongation at Break.
Each of these tables include data on the effects on a single parameter
of the immersion of all of the liners in all of the wastes. The data on
dimensional changes are reported in percent changes in machine and trans-
verse directions measured at the top and bottom of the immersed specimens.
The data on the elongation at break and stress at 100% elongation are
based upon averages of the data obtained in the machine and transverse
directions. These data are reported as a percent retention of the original
properties. The results of the immersion tests are discussed by polymeric
membrane type.
Butyl Rubber (IIR)
Two sets of specimens of an unreinforced butyl sheeting (No. 44)
were exposed in 13 different wastes or test media from 174 to 1456 days.
Exposure in each waste was for two elapsed times in all of the wastes
except the Basin F waste, in which only one set of specimens for most
materials were immersed since only one cell of the Basin F waste was
available for testing. All of the liners showed only small weight changes
in the early part of the exposure; consequently, the exposure was continued
in most cases for approximately 1200 days before the specimens were removed
and cut for physical testing.
The specimens of the butyl membrane increased in weight during ex-
posure from about 1% to more than 100%. The butyl specimens increased in
weight in all wastes with the greatest increases in those specimens that
had been immersed in the oily wastes, the aqueous solution containing
tributyl phosphate, and the lead waste. The oily wastes and the lead waste
caused the butyl specimens to swell significantly.
Note: Combinations testing the butyl liner with the oily wastes
had been deleted from the primary tests because of the
results of the preliminary compatibility study.
The changes in dimension were almost all positive and similar in both
directions indicating that the strains introduced during calendering
relaxed during the vulcanization of the sheeting.
The extractables contents after immersion ranged from 10.62% for the
specimen immersed in the acidic waste "HFL" for 761 days to 40.34% for the
specimen immersed in the "Oil Pond 104" waste for 752 days. Compared with
the 11.8% value for extractables of the unexposed sheeting, these results
indicate that the plasticizer in the butyl compound, usually a hydrocarbon
oil, does not appear to migrate to the aqueous wastes.
"Oil Pond 104" waste caused the greatest swelling of the butyl mem-
brane and had the greatest effect upon the membrane resulting in substan-
tial losses of properties.
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Chlorinated Polyethylene (CPE)
Two types of CPE sheeting were immersed. One (No. 77) was an unrein-
forced thermoplastic sheeting of 29 mil thickness and the second (No. 100)
was a crosslinked CPE of 36 mil thickness. Liner 77 was also studied as a
primary liner. Liner 100 was added to assess the effect of crosslinking
the CPE upon the interaction of CPE membrane with wastes.
Except for a small loss in weight of the crosslinked CPE specimens
immersed in slopwater and in brine (5% NaCl), all of the CPE specimens
increased in weight. As indicated by the volatiles results, which were
determined by heating the sheeting, much of this increase in weight was
through the absorption of water.
A major difference between the thermoplastic and crosslinked CPE
liners was apparent in the dimensional changes that took place during
immersion. The crosslinked CPE (No. 100) increased in dimensions approxi-
mately equally in the machine and the transverse directions whereas the
thermoplastic CPE (No. 77) increased more in the transverse direction and
in some cases simultaneously shrank in the machine direction and expanded
in the transverse direction.
As was anticipated, the crosslinked CPE increased less in weight on
immersion in the wastes than did the thermoplastic uncrosslinked sheeting.
However, the effects of swelling did not necessarily carry over into the
physical properties as can be seen by an inspection of the data in Appendix
J-6 (Retention of Stress at 100% Elongation). In the case of the samples
in the nonoily wastes, both the crosslinked and the thermoplastic sheetings
tended to increase in modulus (S-100), i.e. to stiffen, with exception of
the crosslinked CPE immersed in the acidic wastes. The thermoplastic CPE
tended to stiffen more than the crosslinked CPE. Of the samples immersed
in the oily wastes, even though both sheetings lost in modulus, the reten-
tion of S-100 was significantly less for the thermoplastic CPE than for the
crosslinked. The thermoplastic CPE lost severely on exposure to the
"Slurry oil" waste, the lead waste, the "Weed oil" waste, and the trace
organic solution. The "Weed oil" waste appeared to have completely dis-
solved the thermoplastic CPE specimen. The retention of elongation at
break was generally less than 100% and was about equal for the thermo-
plastic and crosslinked compounds.
Chlorosulfonated Polyethylene (CSPE)
Two versions of a CSPE lining material produced by the same manufac-
turer were immersed in the 13 wastes or test media for two time periods,
the shorter time period ranging from 174 to 522 days and the longer from
751 to 1456 days. One membrane was a fabric-reinforced sheeting (No. 6R)
which had been previously tested in the study of lining materials in
contact with MSW leachate (Haxo et al, 1982) and as a liner for the primary
exposure test cells in this project. The second was an unreinforced CSPE
sheeting (No. 55) of 35-mil thickness. Both were "potable" grade CSPE
compounds.
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Overall, the two CSPE materials responded very similarly to the
wastes, even though one contained fabric reinforcement and the other did
not. All of the specimens in immersion swelled and gained in weight, with
the samples immersed in the oily wastes increasing the most. These in-
creases ranged from 30% to more than 350%. In the predominantly aqueous
wastes, the weight increases and the amount of water absorbed as indicated
by the volatiles were less significant. Furthermore, the weight increases
of the specimens immersed in deionized water were greater than those im-
mersed in wastes and liquids containing high salt concentration, e.g. the
"Spent caustic" waste. Analysis for extractables indicated that the ex-
tractables increased only among those specimens immersed in the oily
wastes. The specimens immersed in aqueous wastes had approximately the
same extractables as the unexposed sheeting. This indicates that the loss
of plasticizer to the waste is low.
The "Weed oil" waste was by far the most aggressive toward this lining
material resulting in significant losses in modulus. Losses in modulus
(S-100) were much less in the other oils and not to the extent that might
be anticipated from the swelling. These materials appear to have cross-
linked during the immersion.
With respect to the other nonoily wastes, the increase in weight
ranged from approximately 2.2 to 20%, with major increases in stiffness,
i.e. S-100, and in some cases loss in elongation, such as in the slopwater.
Again, this reflects the crosslinking reaction that took place during the
immersion.
These data generally indicate the need for compatibility testing of
CSPE liners in wastes with which they might be used and that long exposures
are probably necessary for the proper assessment of compatibility. Again,
as indicated above, both of these CSPE sheetings were based on potable
grade CSPE compound. The more recently developed industrial grades should
show significantly less adverse effects on exposure to wastes such as were
used in this project.
Elasticized Polyolefin (ELPO)
Two sets of specimens of a single elasticized polyolefin sheeting (No.
36) was immersed in the 13 wastes and test fluids for two time periods.
The shorter time period ranged from 174 to 522 days, and the longer from
751 to 1456 days (Appendix J-l).
Almost all specimens gained some weight; those specimens immersed in
the aqueous liquids tended to gain the least and those immersed in the oily
wastes gained the most. Those specimens immersed in the saturated tributyl
phosphate solution had intermediate gains in weight. Among the nonoily
wastes, the slopwater, which was a highly alkaline material, caused a
substantial weight increase in this sheeting. These weight increases were
reflected in the retention of stress at 100% elongation (S-100). The
specimens that increased in weight tended to soften, i.e. had lower reten-
tion values. The retention of elongation at break varied more but in most
cases the retention was lower with the more swollen specimens.
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The main conclusion to be drawn from the immersion tests of the
elasticized polyolefin is that this sheeting should not be used in contact
with hydrocarbon oily wastes, with wastes that are highly alkaline and
possibly those wastes that are highly acidic. Also, if this membrane is
being considered as a lining of an impoundment of waste liquids, its
compatibility with the waste over an extended period of time should be
determined.
Ethylene Propylene Rubber (EPDM)
Two sets of specimens of two sheetings were immersed in the 13 waste
liquids and test fluids for two time periods. The shorter time period
ranged from 174 to 522 days and the longer period from 751 to 1456 days.
One sheeting was crosslinked EPDM (No. 91) and the second was a fabric-
reinforced (8 x 8, polyester) thermoplastic sheeting (No. 83R).
The response of these sheetings to the wastes was generally differ-
ent though in some "wastes", e.g. in deionized water, the two responded
similarly.
Contrary to what would normally be expected, the thermoplastic EPDM
sheeting (No. 83R) absorbed less waste and retained its properties better
than the crosslinked EPDM sheeting (No. 91). Even in the case of the oily
wastes, the absorption was generally less.
In the case of the nonoily wastes, the crosslinked EPDM increased
significantly more in weight in the acidic wastes and in the "Weed killer"
waste. This appears to reflect the sensitivity to moisture on the part of
this sheeting.
The volatiles after immersion indicate that, in most cases, the weight
increases were due to water absorption, particularly in the crosslinked
specimens immersed in the acidic wastes. The extractables data indicate
that little if any of the plasticizer in the original compounds was lost to
the waste. The only specimens that increased in extractables were those
that had been immersed in the oily wastes.
The effects of the immersion on stress at 100% elongation generally
reflected the amount of weight increase, particularly for those specimens
immersed in the oily wastes and the crosslinked EPDM immersed in the
"HNOs-HF-HOAc" acidic waste.
The effects of the immersion on elongation were highly variable with
retentions varying from 47 to 154%. The elongation of the thermoplastic,
fabric-reinforced sheeting increased in all cases, whereas most of the
crosslinked specimens immersed in the oily wastes lost in elongation.
Neoprene (CR)
Two sets of specimens from one neoprene liner (No. 90) were immersed
in the 13 wastes and test liquids from 174 to 1456 days. All of the
specimens gained weight on immersion and the weight gains were the greatest
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in the oily wastes. The smallest weight increases occurred in those wastes
that had a high content of dissolved inorganic salts, such as the brine and
the alkaline wastes. The intermediate weight losses occurred in specimens
exposed in those wastes that were predominantly water with low dissolved
salts or acids, for example, the pesticide and "HFL" wastes. As is charac-
teristic with neoprene compounds, the specimens in solutions containing
dissolved inorganic salts swelled less than the specimens immersed in
deionized water.
The effects upon the stress at 100% elongation more or less followed
the increases in weight, that is, the swelling of the neoprene specimens.
The losses in modulus were the greatest in those specimens exposed to the
oily wastes. On the other hand, the neoprene specimens retained less than
100% of their original elongation at break on exposure to all the wastes,
with values ranging from 47 to 98%. The magnitude of retention varied
considerably and did not follow the weight increases.
Overall, this neoprene membrane was sensitive to the oils and to
water. Since, in most cases, the effect increased with time, low reten-
tions may occur on extended immersions. This particular neoprene compound
contained a high level of extractables (21.5%) which may have adversely
affected its performance in these tests.
Polyester Elastomer (PEL)
Two sets of specimens of the experimental polyester elastomer film
(No. 75) were immersed in the 13 wastes and test liquids. The specimens
increased in weight on immersion in all but possibly two of the wastes.
These losses were minor and may have been within experimental error. The
polyester elastomer specimens gained weight principally in the hydrocarbon
oily wastes; the gain in weight in the solution containing tributyl phos-
phate was not as great. The specimens immersed in the acidic waste
"HNOi-HF-HOAc" gained weight significantly; in addition, they lost severely
in elongation as had the same sheeting in the primary cells. This dete-
rioration was the result of the hydrolysis of the polyester polymer.
The retention in stress at 100% elongation of the polyester elastomer
film, tended to be inverse of the increases in weight; that is, the modulus
retention decreased with the increase in weight. Except for the loss in
elongation in the acidic waste, which was drastic, the retention of elonga-
tion was good.
Note: This membrane did not have as good resistance to oil as had
been indicated by the supplier. However, according to the
supplier, new versions are now available with improved pro-
perties.
Polyethylene (PE)
Neither the high- nor the low-density polyethylene immersed in this
study were commercial lining materials and both were nonpigmented. Both
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sheetings exhibited comparatively low values for weight increases in all
wastes. However, as with the other polymeric membranes, the weight in-
creases, though low, were the greatest in the specimens exposed in the oily
hydrocarbon wastes in which the low-density polyethylene sheeting increased
in weight more than the high-density polyethylene. The saturated tributyl
phosphate solution caused only a slight increase in weight, that is 0.3 to
0.5%. The weight increases in all the other wastes were less except for
the low-density polyethylene exposed to "Slopwater" waste.
For the first set of exposed polyethylene samples, the tensile tests
were run at 20 inches-per-minute (ipm) such as are performed on rubber
compounds; however, this speed was not standard for the polyethylenes and,
consequently, the second set was run at 2 ipm and the tensile properties on
the unexposed membranes were redetermined at 2 ipm. The retention of
elongation of the high-density polyethylene sheeting on the longer expo-
sure periods varied considerably; for example, some major losses in elong-
ation occurred in the samples that had been exposed to the acidic waste
"HN03-HF-HOAc". These major losses in elongation reflect the sensitivity
of the specific polyethylene to specific wastes.
Note: As indicated above, the sample of high-density polyeth-
ylene (No. 105) investigated in the immersion test was
not a commercial lining material, nor was the grade of
HOPE known to have been used in the manufacture of mem-
brane liners. We later found by differential scanning
calorimetry that it was considerably more crystalline than
grades of polyethylenes used in lining materials, had a
higher density, and a considerably higher modulus of
elasticity than the modulus of the HOPE used in liners
that are now available. We also found that the HOPE (No.
105) showed indications of inadequate resistance to
environmental stress-cracking compared with the HOPE
currently used in liners. In a stress-cracking test, the
HOPE sheeting (No. 105) was tested in accordance with ASTM
D1693 but at a thickness of 30 mils, which is below the
required thickness for this test. It sustained some early
breaks (216 h) at 100°C, whereas currently-available HOPE
liners tested at thicknesses of 80 and 100 mils did not
fail in 1,000 hours at 100°C. At the present state of
knowledge of HOPE liner performance, specific correlations
between environmental stress-cracking resistance under
different conditions and field service of liners have not
been established.
In the immersion test, the polyethylenes showed low weight increases in
all of the wastes and fluids. The low retention of elongation of the
particular HOPE that was tested indicates the need for carefully select-
ing the type of HOPE to be used in the manufacturing of liners for waste
impoundment facilities. The data show that some grades of HOPE are prob-
ably inadequate for use in liners.
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Polypropylene
The polypropylene (No. 106) studied in this immersion test also was
not a liner material, but, as indicated in the discussion of immersion
combinations, it was a nonpigmented propylene sheeting purchased from a
local plastics supply firm. In the initial tensile testing, it was treated
as a rubber and tested according to ASTM D412 at 20 ipm. In subsequent
tests, the rate of testing was reduced to 2 ipm. During the immersions the
weight increases were small and generally less than those of polyethylene.
As with the other sheetings, the increases were the greatest in the oily
wastes (6-9% in 1250 days). In the other wastes, the changes were less
than a percent and, in some cases, there were small losses in weight which
may be within experimental error.
In the short-term tests in which the testing was done at 20 ipm, the
elongations were all less than 100%. After the longer immersions, the
tests were run at 2 ipm which yielded elongations of 650% and greater.
Retention of elongation based on the unexposed materials using the 2 ipm
gave results of 92 to 112%, except for the specimen immersed in the in-
dustrial waste, Basin F, in which the retention was 76% after 1287 days of
exposure.
Overall, this polymeric sheeting retained its properties well after
exposure to the various wastes, although the effects of the oily wastes are
measurable. This material, however, has not been commercialized in the
United States and none was available as a liner material for testing. The
tests we performed on this non-liner propylene show that this highly
crystalline polymer is quite compatible with many wastes.
Note: This particular polypropylene sample cracked relatively
early in the environmental stress cracking test, ASTM
D1693; thus, this grade of polypropylene would probably
not be satisfactory as a lining material.
Polyvinyl Chloride (PVC)
Three different PVC membranes were immersed in the 13 wastes and test
liquids from 174 to 1456 days. The three (Numbers 11, 59, and 88) repre-
sented PVC membranes from three different suppliers and were 22, 33, and
20 mils in thickness, respectively. Liner No. 59 was tested as a primary
liner in the project. These three PVC membranes differed considerably
among themselves and in their responses to the different wastes.
The changes in weight during immersion ranged from significant loss,
i.e. 15.7%, to substantial gains, i.e. 57.7%, depending on the waste liquid
and the immersion time. All three sheetings lost weight in the slopwater,
the brine, and "Oil Pond 104" waste. In water they all initially increased
in weight and then lost weight. In other wastes, some gained and others
lost weight. All gained in volatiles content which reflects the absorption
of water from the wastes. Analysis of the extractables after removal of
the volatile constituents indicates that in several cases there was sub-
stantial loss in the original plasticizer, such as was the case with the
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specimens immersed in slop water. In some cases, the extractables content
increased due to the absorption of nonvolatile organics, e.g. hydrocarbon
oils.
The effects upon the dimensions of the immersed specimen were quite
varied but generally followed the weight changes, i.e. if the specimen
gained weight the dimensions increased. If the specimen lost weight, it
decreased in length and width. In the case of shrinkage, a confined
sheeting would come under tension and a hole would become enlarged. There
appeared to be a dimensional effect; the dimension in the transverse
direction tended to increase more and shrink less than the dimension in the
machine direction.
The effects upon properties appear to correlate reasonably well with
the weight changes. Those specimens that lost weight all became harder as
shown by the retention of stress at 100% elongation; those that increased
in weight generally became softer. The effects of weight loss also show up
in the retention of elongation for those materials that lost substantially
in plasticizer and which not only became stiff, but lost in elongation.
Overall, the PVC lining materials varied considerably in their res-
ponse to different wastes. Certain wastes, such as the highly alkaline
wastes, are particularly aggressive toward the PVC and certain oils can
cause loss of plasticizer and excessive stiffening and loss of elongation.
Concurrent with these losses, the PVC sheeting can shrink and develop
tension in the sheets. It is quite apparent that, if a PVC membrane is
being considered for the lining of an impoundment that would contain
potentially polluting waste, its compatibility with that waste should be
determined.
IMMERSION OF MEMBRANES IN SATURATED AQUEOUS
SOLUTIONS OF TRIBUTYL PHOSPHATE
The tendency of organic lining materials, such as asphaltic and
polymeric membrane liners, to absorb dissolved organic constituents of a
waste liquid, even from dilute aqueous solutions, can have a highly signi-
ficant effect upon liners on long exposures. This effect was observed with
the asphalt concrete liner below the lead waste which contained a low
concentration of oily components. It absorbed oily constituents and became
soft and mushy.
Most waste liquids contain small amounts of organics that can be
slowly absorbed by a polymeric material. The amount that can be absorbed
by the liner ultimately depends on the polymer, the compound, and the
chemical characteristics of the organic compounds in the waste. To demon-
strate this effect, a simple "waste" and "exposure" test was conducted in
which two sets of specimens of each of the 16 membranes were immersed in a
dilute (<0.1%) but saturated aqueous solution of tributyl phosphate (TBP)
in deionized water. TBP was selected for this study, not only because of
its low solubility in water, but also because of its relatively low vola-
tility and its phosphorous content which could be used as a tracer of the
TBP movement. The concentration of TBP was maintained in the water by
150
-------
hanging highly TBP plasticized disks of PVC in the tanks in which the
specimens were immersed. The detailed results are presented in Appendixes
J-l through J-7.
The first immersion exposure was 522 days and the second ranged from
1035 to 1119 days. On removal from immersion, the following parameters, as
indicated above, were measured: weight change, extractables, volatiles
(water), tensile strength, elongation at break, modulus of elasticity (for
crystalline materials), hardness, tear (for all but fabric-reinforced
materials), and puncture resistance.
The thermoplastics, i.e. PVC, CPE, and CSPE, increased significantly
in weight and lost considerably in tensile strength and hardness. The vul-
canized CPE sustained less change than the thermoplastic CPE composition.
The neoprene liner, though vulcanized, swelled considerably and lost in
tensile strength and hardness. The butyl and EPDM liners, also vulcanized,
swelled to some extent and sustained only modest losses in properties.
The increase in weight of the samples during exposure in the saturated
solution of TBP is made up of water and dissolved TBP. The total is the
net of the water and TBP that are absorbed minus the plasticizer in the
original compounds that may be lost to the solution.
The question remained as to how much of the original plasticizer
migrates into the solution and is lost by the liner. To answer this
question, analyses of two exposed liners were performed, in which the
extractables obtained after the removal of water from the liner were
analyzed for total TBP content, and calculations were made of the plasti-
cizer remaining in the exposed liner. The results are shown in Table 46.
These results indicate that the original plasticizer in both of these
sheetings was retained during exposure and that the entire increase in
extractables was a result of the absorption of the TBP.
Inspection of the data in Appendix J-3 regarding the immersion of the
liner samples in saturated TBP indicate that the increase in weight tends
to level off in most of the specimens. It thus appears that a maximum
value of swelling may be achieved for a given organic chemical. However,
these results are not confirmed by the data on volatiles (Appendix J-4)
which tend to show that the volatiles increase with time.
Of particular interest are the low swelling and small losses in
the values of the physical properties incurred by the semi crystal line
polymers, thus showing the resistance of these materials to the absorption
of an organic chemical such as TBP during the exposure to waste liquids
containing minor amounts of organics.
Neither of the two polyethylene sheetings nor the polypropylene
sheeting tested in this study were commercial liner membranes, but two
semi crystal line polymers, HOPE and LDPE, are used currently in the manu-
facture of liner membranes. These three semi crystal line sheetings were
tested so that comparisons could be made with other polymeric materials of
the same thickness.
151
-------
TABLE 46. ANALYSES OF CHLORINATED POLYETHYLENE AND POLYVINYL CHLORIDE
MEMBRANES EXPOSED IN SATURATED TBPa SOLUTION
Liner number
Extractables of unexposed liner, % by
weight of the original liner
Exposure time, days
Extractables after exposure, % exposed
membrane after volatiles were removed*3
TBPC, % exposed membrane (dvb^)
Extractables, TBP, %
Calculated plasticizer in original
sheeting, % based on polymer
content and plasticizer
Chlorinated
polyethylene
77
9.13
1112
26.1
19.8
6.3
9.4
Poly vinyl
chloride
59
35.9,37.4
1055
51.7
23.3
28.4
36.4
aTributyl phosphate.
^Specimens previously tested and held in sample storage file.
cAnalyses of extract by gas chromatography.
= devolatilized basis.
152
-------
SECTION 8
OUTDOOR EXPOSURE TESTS OF POLYMERIC MEMBRANE LINERS
INTRODUCTION
In many actual waste storage facilities it is desirable to leave the
membranes uncovered, that is, without soil covers. Consequently, in
addition to being exposed to the impounded liquid or sludge, part of the
membrane, such as that on a berm, may be exposed to weathering. In such
situations, the lining material is exposed to ultraviolet light, heat of
the sun, wind, ozone, fluctuations in temperature, and to rain, hail, and
ice. These conditions can cause some polymeric materials to degrade,
resulting in softening or hardening and possibly in breakage of the liner.
Membrane liners that are sensitive to these conditions are normally covered
with soils to avoid the adverse effects of the weather.
In this project it was desired to develop information on the full
characteristics of liners, including some of their basic limitations.
Consequently, weather exposure tests were included in the program, although
some of liners, for example polyvinyl chloride, are normally not exposed to
the weather except for short durations.
It is recognized that geographic location can affect the weather
conditions greatly; however, these test were undertaken to compare the
materials. (Estimating service life of a material in outdoor conditions
requires that tests be conducted in weather that is similar to the antici-
pated actual service.)
Two types of outdoor exposure tests were undertaken, both of which
involved exposing samples of the membranes on the roof of the laboratory in
Oakland, California. These tests were:
- Exposure of small slabs of polymeric membranes on a rack and remov-
ing them periodically to measure the effects of the exposure on
properties.
- Exposure of samples of the membranes as linings of small tubs in
which different wastes were loaded and maintained at more or less
constant level.
These methods are described and the test results are presented in the
following subsections.
153
-------
ROOF RACK EXPOSURE
In the roof rack exposure, 6x6 in. specimens of 11 different poly-
meric membranes were exposed on a rack placed on the laboratory roof in
Oakland, California, at a 45° angle to the south. Three specimens of each
membrane material were hung on boards so that only one side was exposed to
the sun. The rack with the test specimens is shown in Figure 23. The
specimens were hung loosely to allow them to change dimensions freely.
These 11 membranes were based upon the following polymers:
Butyl rubber, fabric-reinforced
Chlorinated polyethylene
Chlorosulfonated polyethylene, fabric-reinforced
Elasticized polyolefin
Ethylene propylene rubber (2 membranes)
Neoprene (2 membranes)
Polyester elastomer
Polyvinyl chloride (2 membranes).
Figure 23. Exposure rack loaded with polymeric membrane specimens. The
rack is exposed at a 45° angle to the south.
One specimen of each of the membranes was removed after 343, 745, and
1231 days and the following properties were determined:
Wei ght
Dimensions
Volatiles
Extractables
154
-------
Hardness
Tensile strength
Elongation
Tear strength.
Changes in surface characteristics, including cracking and checking, were
observed. Changes in these parameters and properties are reported in
Appendix K.
Results
Results of 1231 days of weather exposure are presented in Table 47.
They illustrate some of the differences in the weatherability of different
polymeric membranes. Some of the major effects of the exposure were:
1. With only a few exceptions, the specimens lost weight and extract-
ables content; the largest losses were sustained by the two PVC
liners which lost plasticizer. The CSPE increased in weight,
perhaps due to moisture absorption. The polyester elastomer
membrane lost significantly in weight and, at the same time,
increased in extractables content which may indicate some degrada-
tion of the polymer.
2. The moduli of all membranes increased. The amount and mechanism
of increase varied with the individual membrane. The CSPE and PVC
liners increased the most, and one EPDM, the elasticized poly-
olefin, and the polyester increased the least. The increase in
modulus by the CSPE membrane was the result of crosslinking which
took place during the exposure period; on the other hand, the
increases in the moduli of the PVC membranes were due to loss of
plasticizer as shown by the loss in weight and the reduced ex-
tractables content.
3. All membranes except that of butyl rubber lost in elongation. The
butyl rubber membrane was reinforced with a fabric which control-
led the elongation at break. The CSPE and neoprene membranes
sustained the greatest losses.
4. The surfaces of all of the membranes changed little during the
exposure, except for the PVC which crazed or "al1igatored".
Obviously, thinner PVC sheeting would have been seriously affected
by the exposure of 1231 days.
TUB TEST
The second type of outdoor exposure test was the tub test in which
small tubs lined with different polymeric membranes and partially filled
with wastes were exposed to the weather. The objective of this test was
to test polymeric membrane liners under conditions that simulated some of
the conditions that exist in an open lined impoundment in which the liner
is not covered with soil. The effects of exposure to sun, temperature
155
-------
TABLE 47. OUTDOOR EXPOSURE OF POLYMERIC MEMBRANE LINERS ON ROOF RACK IN OAKLAND, CALIFORNIA FOR 1231 DAYS
Unexposed membrane
Liner data
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized
polyolefin
Ethylene pro-
pylene rubber
Ethylene pro-
' pylene rubber
en
cr»
Neoprene
Neoprene
Polyester
elastomer
Polyvinyl
chloride
Polyvinyl
chloride
Numberb
57R
77
6R
36
8
26
43
82
75
11
59
Thickness,
mil
34
29
31
22
62.5
30
34
60
7
30
33
Compound
typec
XL
TP
TP
CX
XL
XL
XL
XL
CX
TP
TP
Extractables,
6.4
9.1
3.8
5.5
23.4
23.0
13.7
13.4
2.7
33.9
35.9
S-1003,
psi
d
1180
938
932
335
358
460
383
2585
1420
995
Elongation
at break3,
42
403
243
665
510
450
320
400
575
357
375
Weight
change, %
-3.32
-3.15
+ 1.80
-1.93
-3.91
-3.11
-3.11
-1.31
-6.23
-15.61
-10.31
Exposed membrane
Extractables,
5.7
6.3
3.3
5.3
21.3
21.8
9.9
11.5
3.9
26.3
27.8
Retention of property3, %
S-100
d
139
248
119
142
119
184
188
110
161
185
Elongation
at break
102
81
52
95
91
94
63
63
83
77
86
'Properties of the lining materials measured in both machine and transverse directions and reported as an average or based on the average.
^Matrecon identification number; R = fabric-reinforced.
CXL = crosslinked or vulcanized; TP = thermoplastic; CX = crystalline.
dSpecimen broke at less than 100%.
-------
changes, ozone, and other weather factors can be assessed as well as the
effect of a given waste on a specific liner. The fluctuation in the level
of the waste is particularly significant in that an area of the liner is
subjected to both the effects of the waste and the weather. Generally,
this alternating of conditions is especially harsh on a polymeric liner
material, but such conditions usually are encountered in the field in open
ponds where the liners are not covered with soil.
Description of the Tubs
The tubs were constructed of 0.75 in. exterior grade plywood with
sides sloping outward at a 1:2 slope. The opening at the top was 20 x
25 in. and on the inside base was 7.13 x 12 in. The depth of the tub was
10 in. A sketch of the tub is shown in Figure 24 and a photograph of six
of the tubs in a catch basin is shown in Figure 25.
TOP VIEW
7"
12"
19.75"
ISOMETRIC DRAWING OF TUB
(Sketch not to scale)
24.5"
24.5'
10"
8"
(varies)
8.75" '
FRONT VIEW
SIDE VIEW
Figure 24. Drawing of the tub used in the roof exposure of polymeric
membrane liners in contact with wastes.
157
-------
Figure 25. The open exposure tubs lined with polymeric membranes and
partially filled with hazardous wastes. They were covered
with chicken wire and placed in a lined shallow basin.
Test Procedure
The combinations of the liner specimens and wastes that were selected
for this test are shown in Table 48. The test specimens consisted of a
sheet 40 x 48 in. which, in most cases, incorporated a seam through the
center. In this way the seam durability as well as that of the liner was
assessed. The test specimens were draped over the tubs and folded to fit
the inside corners and edges of the tubs; the excess material was allowed
to hang freely over the edges. In this manner, there were a considerable
number of folds and sharp angles to which the liners were exposed, parti-
cularly over the corners of the tubs. If the membrane was sensitive to the
waste or to the ozone, cracking or crazing would develop.
The tubs were filled from 3/4 to 7/8 full with wastes. The liquid
level was allowed to fluctuate about 4 in. Approximately 4.5 gallons of
waste was required to fill a tub.
Monitoring
During the exposure the tub liners were regularly inspected visually
for cracking, opening of seams, and other forms of liner deterioration.
During the rainy periods, the tubs were covered. The waste levels and
temperatures were measured and recorded at regular intervals. Water was
added when levels became too low.
158
-------
TABLE 48. COMBINATIONS OF POLYMERIC LINERS AND WASTES PLACED IN TUB TEST
Waste identification
Acidic
Alkaline
Polymer
"HN03-HF- "Slop- "Spent
HOAc" water" caustic"
Number3 (W9)b (W4)b (W2)b
Oily
"Oil Pond
104"
(W5)b
Butyl rubber 57R
Chlorinated polyethylene 77
Chlorosulfonated poly-
ethylene
Elasticized polyolefin
Ethylene propylene rubber
Neoprene
Polyester elastomer
Polyvinyl chloride
6R
36
8
82
75
11
59
XX-
X
X - X
_
_
X - -
-
X
-
X
X
X
aMatrecon liner serial number; R
^Matrecon waste serial number.
= fabric-reinforced.
The shallowness of the tubs and the dark color of the liners resulted
in high heat absorption when the tubs were exposed to sunlight; the liners
and the wastes were quite warm on sunny days. The temperature -"
tored regularly and the high and low temperatures in
are shown in Table 49.
the
was
different
moni -
cells
During much of the year, the oily wastes accumulated water (from dew)
on the bottom of the tubs and did not evaporate significantly. Water, or
actually an oil-water mixture, had to be pumped from the bottom of the tubs
to maintain liquid levels and prevent overflows of the waste. The oil-
water mixture was removed and analyzed for pH, electrical conductivity,
percent solids, and other parameters as appropriate. During the rainy
period, water in the catch basin was also monitored for pH and conductivity
as a possible indication of leakage from the tubs containing highly acidic
or highly alkaline wastes.
Results
Since the time that the tubs were placed in exposure in November 1976,
only three tubs have been removed (June 1983) from service and the liners
tested. All three were removed because of failures of the liners; two
were lined with elasticized polyolefin and contained "Oil Pond 104 "waste.
159
-------
TABLE 49. TEMPERATURE OF WASTES IN TUBS ON ROOF OF LABORATORY IN OAKLAND, CALIFORNIA
CTi
O
At lowest observed temperature3
Tub
le
2
3
4
5
6
7
8
9
10
11
12
if
Date
filled
11/2/76
11/2/76
11/2/76
11/2/76
11/2/76
11/2/76
11/6/76
11/6/76
11/6/76
11/6/76
11/6/76
11/6/76
4/6/78
Liner
Polymer (No.b)
Polyolefin (36)
PVC (59)
Polyester (75)
CSPE (6)
Butyl (57R)
Neoprene (82)
EPDM (8)
Polyolefin (36)
CPE (77)
CSPE (6R)
EPDM (8)
PVC (11)
Polyolefin (36)
Waste (No.c)
"Oil Pond 104" (W-5)
"Oil Pond 104" (W-5)
"Oil Pond 104" (W-5)
Slopwater (W-4)
Slopwater (W-4)
"Oil Pond 104" (W-5)
Spent caustic (W-2)
Spent caustic (W-2)
Spent caustic (W-2)
HN03-HF-HOAC (W-9)
HN03-HF-HOAc (W-9)
HN03-HF-HOAc (W-9)
"Oil Pond 104" (W-5)
Waste,
°C
13.1
12.8
12.8
13.3
13.1
12.8
11.1
10.8
11.1
10.0
10.0
10.0
15.5
Date
10/14/77
10/14/77
10/14/77
10/12/77
10/12/77
10/14/77
10/12/77
10/12/77
10/12/77
10/12/77
10/12/77
10/12/77
5/10/78
Ambient,
°C
12.8
12.8
12.8
16.1
16.1
12.8
16.1
16.1
16.1
16.1
16.1
16.1
18.3
Condi -
tiond
STF
STF
STF
ST
ST
STF
ST
ST
ST
ST
ST
ST
ST
At highest observed temperature3
Waste,
°C
65.6
66.1
65.6
50.0
50.6
66.1
51.1
51.7
51.1
43.5
44.0
46.0
46.5
Date
7/29/77
7/29/77
7/29/77
7/29/77
7/29/77
7/29/77
7/29/77
7/29/77
7/29/77
6/7/77
6/7/77
6/7/77
8/18/78
Ambient,
°C
38.3
38.3
38.3
38.3
38.3
38.3
38.3
38.3
38.3
28.6
28.6
28.6
29.0
Condi -
tiond
B
B
B
B
B
B
B
B
B
U
U
U
B
aHighest and lowest temperatures of the wastes observed from the times the tubs were filled until September 2, 1978.
^Matrecon liner serial number; R = fabric reinforced.
°Matrecon waste serial number.
dWeather condition:
ST = Still air; no breeze.
STF = Still air and foggy.
B = Breezy
U = Unknown - not recorded.
^Failed; dismantled on March 23, 1978.
^Replacement; first liner failed March 23, 1978 and was replaced.
-------
This liner material had not been recommended for oily applications; how-
ever, it had functioned satisfactorily in preliminary compatibility tests.
Both of these liners failed by cracking at folds. The third liner that had
to be removed because of failure was a neoprene liner from the tub that
contained the oily waste, "Oil Pond 104". The recovery and testing of each
of the liners is described and discussed in the next three subsections.
Recovery and Testing of First Failed Elasticized
Polyolefin Liner Exposed to "Oil Pond 104" Waste--
The elasticized polyolefin liner exposed to "Oil Pond 104" waste
failed after 506 days of exposure at a crack in a fold at the interface
between the air and the waste at the waste surface on the north sloping
side of the tub. The liner appeared to have swelled considerably in
this area. On removal from the tubs, physical tests were performed at four
exposure locations:
- Under the waste at the bottom of the tub.
- In the waste-shade zone on the south side.
- In a shade zone only where the sheeting was draped over the north
edge.
- In a waste-sunlight zone on the north side.
The waste-sunlight zone provided the most severe environment for the liner
material.
The results of the tests made at the various locations are presented
in Table 50. They are reported as retention of values of the original
unexposed material.
As can be seen from the data, those portions of the liner that were in
contact with the waste, and particularly at the air-waste interface, lost
significantly in tensile strength and modulus. On the other hand, the
portion of liner that was not in contact with the waste and was facing away
from the sunlight retained properties.
Recovery and Testing of the Second Failed Elasticized
Polyolefin Liner Exposed to "Oil Pond 104" Waste--
This elasticized polyolefin liner replaced the first liner (above)
that had failed. It did not have a seam. The second liner failed after
1308 days of exposure in much the same fashion as the first. It cracked
at a fold at the surface of the waste where the fold had been intermit-
tently in contact with the waste.
On removal from the tub, this membrane showed considerable distortion
and swelling at the air-waste interface area. Testing was performed in
161
-------
TABLE 50. RESULTS OF TUB TEST OF FIRST ELASTICIZED POLYOLEFIN MEMBRANE
EXPOSED TO AN OILY WASTE ("OIL POND 104") FOR 506 DAYS3
Effect of Location and Exposure in Tub
% Retention of property of exposure
Test
Thickness, mil
Tensile strength, psi
Elongation at break, %
Tensile set, %
S-100, psi
S-200, psi
Puncture resistance, Ib.
Elongation, in.
Origi nal
value
23
2525
655
445
905
1000
26.3
0.97
Under
waste^
113
48
90
76
66
62
97
130
In waste
and
sunc
113
39
82
72
57
58
73
122
In waste
and
shaded
113
46
84
74
62
61
70
113
In
shade6
98
99
101
100
107
104
135
142
aFrom 11/2/76 to 3/23/78. Tensile data reported for transverse
di rection only.
bAt botton of tub.
C0n the north side facing south.
dOn the west side facing east.
eOn the north side on draped section facing north.
accordance with the pattern shown in Figure 26. This pattern features the
removal of a one-inch strip across the north-south axis of the tub. The
thickness of the strip was measured along its length with a roller type
gauge and the results are presented in Figure 27. This pattern also shows
the location of the test specimens that were used.
The test results for the liner samples taken from the different
locations are presented in Table 51 in comparison with the values for the
unexposed material. Again, as with the first failed liner, the effects of
the absorption of the oil are large. The specimens taken from the north
interface had an extractables content of almost 33%, an increase of more
than 20%. Retention of the tensile strength of the liner at the interface
area on both the north and south sides was low. The change in tensile
strength with the change in thickness during exposure caused by swelling or
shrinkage is shown in Figure 28. The data on all of the individual
tensile determinations have been included in the plot.
162
-------
WEST
41"
EAST
EXPLANATION
\ Visible crack!
Area swollen
and wunkled
Smooth area
under waste
Tear d,e C
Tensile
Voldlilei
Punctu.ei
O
Q
Figure 26. Drawing of exposed elasticized polyolefin liner showing
locations where the test specimens were cut and the orienta-
tion with respect to the tub and to the north. Location of
strip for measuring thickness across specimens is also shown.
BOTTOM
(Under waste which
m«y contain water)
SOUTH SOUTH
SIDE Weather
axpo!ed
16 20 24 26
NORTH -*. SOUTH, INCHES
Figure 27. Thickness of strip of exposed elasticized polyolefin liner cut
across the width of the liner in north-south direction.
163
-------
TABLE 51. RESULTS OF TUB TEST OF SECOND ELASTICIZED POLYOLEFIN MEMBRANE
EXPOSED TO AN OILY WASTE ("OIL POND 104") FOR 1308 DAYS ON LABORATORY
ROOF IN OAKLAND, CALIFORNIA9
Variation in Location in Tub
Location in tub
Property
Analytical properties:
Volatiles, %
Extractables, %
Physical properties:
Thickness
Tensile at break
Elongation at break
Tensile set
S-100
S-200
Tear strength
Puncture resistance:
Stress
Elongation
Properties
of unex-
posed liner
0.15
5.50
North
at
top
1.65
7.54
North
at
inter-
face
6.2
32.7
Waste
only
8.6
20.7
South
at
inter-
face
8.4
23.0
Retention, %
23 mil
2620 psi
665 %
465 %
925 psi
1020 psi
380 ppi
26.3 Ib
0.97 in.
98
84
80
92
97
95
94
119
144
112
29
63
62
49
47
41
71
132
107
48
89
80
63
61
56
68
118
112
37
83
76
59
56
48
69
116
aFrom 4/6/78 to 10/1/81; tensile and tear values are averaged for both
directions.
EXPLANATION
O MACHINE DIRECTION
A TRANSVERSE DIRECTION
2 4 B 0 10
PERCENT CHANGE IN THICKNESS
Figure 28. Retention of tensile strength
posed in the oily waste, "Oil
function of change in thickness
of elasticized polyolefin ex-
Pond 104," for 1308 days, as a
due to swelling.
164
-------
Recovery and Testing of the Neoprene
Liner Exposed to "Oil Pond 104" waste--
The neoprene liner was the third to fail in the oily waste, "Oil Pond
104." It failed in the seam. The liner was removed and tested similar-
ly to the second elasticized polyolefin. The results of this testing are
shown in Table 52. The liner absorbed a significant amount of oily waste
as shown by the increase in extractables in the areas where the liner was
in contact with the waste.
TABLE 52. RESULTS OF THE TUB TEST OF A NEOPRENE MEMBRANE AFTER EXPOSURE TO AN OILY WASTE
FOR 2008 DAYS ON LABORATORY ROOF IN OAKLAND, CALIFORNIA
Samples Taken From Different Locations in Tub
;"OIL POND 104")
Property
Properties of
unexposed
liner
South
top
Position in tub
South
slope Bottom
North
slope
North
top
Direction
of test
Analytical properties
Extractablesb, %
Volatiles
Loss over desiccant
13.43
12.28
30.09
25.33
28.94
12.71
at 50°C, %
Physical properties
Thickness (average)
Tensile at break
Elongation at break
Tensile set
S-100
S-200
Tear strength
Puncture resistance
Thickness
Stress
Elongation
Hardness, durometer points
5-second reading
...
0.6
5.1
6.5
2.1
0.5
Retention0, %
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
61 mil
1835 psi
1675 psi
390%
410%
10%
9%
405 psi
360 psi
875 psi
705 psi
185 ppi
180 ppi
60.5 mil
53.9 Ib
1.2 in.
57A
+3
89
89
71
70
130
122
152
146
135
144
88
89
+5
97
51
+7A
+23
51
39
84
79
90
100
40
28
52
42
36
35
+26
54
84
-31A
+26
41
45
79
75
90
77
29
34
44
54
31
29
+29
64
81
-29A
+23
31
43
96
89
80
111
16
29
24
41
36
30
+31
32
73
-33A
+7
85
92
74
70
100
122
154
161
132
155
84
81
+7
102
68
+8A
aCrosslinked (XL) neoprene sheeting of 60 mils thickness, without fabric reinforcement.
bMatrecon Test Method (Matrecon, 1983 - p. 340-343).
cThickness = percent change; hardness = change in points.
Again, the value for the extractables of the sheeting from the bottom
of the tub was lower than that of the sheeting on the sides at the air-
waste interface area. This may be either an indication of the more
severe condition at the interface or the fact that water was at times on
the bottom of the tub which reduces swelling. The retention of physical
properties is indirectly related to the degree of swelling by the oily
waste.
165
-------
There was a seam in this sheeting which was tested
shown in Table 53. The seam under the waste had lost
strength compared with the seam that had not been in
waste.
with the results
severely in seam
contact with the
TABLE 53. SEAM STRENGTH OF NEOPRENE LINER (#82)
AFTER 2008 DAYS OF EXPOSURE IN TUB CONTAINING
OILY WASTE, "OIL POND 104"
Mode of test
Location in tub of sample tested
East West
top Bottom top
Shear
Maximum, ppi
Locus of failure
58.8
AD-LSa
8.1
AD-LSa
55.1
AD-LSa
Peel , ppi
Maximum*3
Average
Locus of failure
9.2
6.5
AD-LSa
1.6
0.8
AD-LSa
8.2
5.5
AD-LSa
aAD-LS = Failure between adhesive and liner surface.
^Maximum is at caulked edge.
Discussion--
The results of the roof tub exposure show the importance of the
location within a waste facility from which the samples are taken. The
aging that occurs at the different locations in the pond can vary con-
siderably, particularly if there is stratification of the waste which
probably occurred with the oily waste. However, the most severe section
was probably at the interface between the waste and the air on the north
slope which faced toward the south.
166
-------
SECTION 9
POUCH TEST FOR POLYMERIC MEMBRANE LINER MATERIALS
INTRODUCTION
Since the permeability of membrane liners to waste liquids and the
dissolved components may not necessarily be reflected by the water vapor
permeability as determined by ASTM E96, other methods of assessing the
permeability of liner materials were investigated. Of these, one of the
most promising was the "pouch test," in which a waste liquid is sealed into
a pouch fabricated from the liner membranes under test and the pouch is
then placed in deionized water that, in turn, is in a closed container.
Such a condition simulates a pond containing a waste. The permeation of
dissolved constituents of the waste liquid through the pouch wall can be
followed by pH and electrical conductivity measurements of the water in the
outer container and the permeation of water into the pouch containing waste
liquid by monitoring the weight of the pouch.
To demonstrate the feasibility of the test procedure, initial experi-
ments were carried out in the study of liners for MSW landfills (Haxo et al,
1983) on two sets of pouches fabricated from heat-sealable liner materials.
One set was filled with MSW leachate and the second set with a 5% aqueous
solution of sodium chloride. The liner materials in these tests included
the following polymers:
- Chlorinated polyethylene.
- Chlorosulfonated polyethylene.
- Elasticized polyolefin.
- Polyester elastomer.
- Polyvinyl chloride (three different membranes).
Results are reported in the final report (Haxo et al, 1983) of that project
and show the feasibility of the test for assessing simultaneously both the
permeability of polymeric membranes to wastes and to some waste constitu-
ents and the effect on a lining material of one-sided exposure to a waste
liquid.
In the case of test pouches containing MSW leachate, after 500 days of
exposure it was apparent that there was movement through the walls of the
pouches by both the water and the dissolved ingredients of the leachate.
167
-------
The electrical conductivity of the water in the outer container increased
indicating permeation of some ions from the leachate in the pouch into the
deionized water; the odor of leachate in the outer water indicated that
some organic constituents in the leachate were also permeating through the
pouch walls. An increase in the weight of the pouches that contained
leachate indicated movement of water through the walls into the pouches.
In that series of tests, the elasticized polyolefin allowed the lowest
transmission of water and dissolved components, and the chlorinated poly-
ethylene appeared to be the most permeable.
BASIC PROCEDURE OF THE TEST
Fabrication and Filling of Pouches
The design of the experiment required that the pouches be liquid-
tight so that whatever passed in or out passed through the pouch walls.
This required liquid-tight seams. Heat-sealing the thermoplastic and
partially crystalline membranes was the most effective method of seaming.
Such seams used the least area and, if made well, appeared to hold up best.
A portable heat-sealing unit, such as is used to make polyethylene bags,
was used. It contained a heating element 13 in. in length.
Note: The unit was a T-Bar Plastic Sealer, Model T13 - 115v AC
130w made by Harwil Co., Santa Monica, California.
This unit was designed primarily for sealing films less than 10 mils in
thickness. Consequently, some problems were encountered in seaming mem-
branes of 30-mil thickness. Longer time, greater pressure, and higher
temperatures were needed to make seams of the thicker materials. Some
seams of thermoplastics, e.g. CSPE, were made with adhesives and solvents.
However, adequate seams of crosslinked membranes could not be made with
two-part room temperature curing adhesives and thus only pouches of thermo-
plastic and crystalline membranes were tested.
Figure 29 is a schematic of the pouch assembly. The dimensions of the
individual pouches varied somewhat but, in most cases, were 18 x 14 cm,
which gave an effective surface of approximately 500 cm2. For the sodium
chloride solution, the pouches were 17 x 12 cm between seams which yielded
an effective surface of approximately 400 cm^.
Except for some of the early pouches, each pouch was constructed with
a neck through which the test liquid could be introduced. Figure 30 shows
a pattern used for cutting and seaming the pouches. The pouch seams were
tested by filling the pouches with water and then letting them stand for
several days. Initially, a relatively large number of pouches failed this
test. To simulate approximately two years of exposure in a moist environ-
ment, the six pouches that were subsequently filled with acidic waste
"HN03-HF-HOAc" were immersed for two weeks in water at 70°C. Deionized
water was added to the CPE pouch after one week to prevent the pouch walls
from sticking together. The soaking of the pouches at 70°C further tested
the integrity of the seams. After a pouch was filled with a waste or test
liquid, as much air as possible was removed and the neck was sealed. Great
168
-------
OUTER BAG-
POLVBUTYLENE
OEIONIZED WATER
IN OUTER BAG
INNER POUCH-
MEMBRANE UNDER TEST
WASTE OR TEST LIQUID
IN THE INNER POUCH
Figure 29. Schematic of a pouch assembly, showing inner pouch made of
membrane material under test. The pouch is filled with waste
liquid and sealed at the neck. The outer polybutylene bag,
which can be easily opened, is filled with deionized water.
The water in the outer bag is monitored for pH and conduc-
tivity; the pouch is monitored for weight change.
Open for waste .
to be added
.
I
* 7 *
[~
5"
,
|
- 1 l
II GRAIN
Jj DIRECTION ||
" ii
1 1
II f I1
II j
! !
i 1
L__ , _J
-* c;y." - K.
7
Figure 30. Pattern for cutting pieces of membranes for making the pouches.
Dotted line indicates the heat seal of the pouch. The inside
dimensions of the pouch are 4.5 in. x 5.75 in. (11.43 x
14.6 cm) which yielded an effective area (2 sides) of ca 52
in.2 (335 cm2).
169
-------
care was taken to keep the inside of the neck dry to ensure a good seal.
Approximately 200 rnL of waste liquid were added to the pouches. Most of
the pouches were heat-sealed and the rest were sealed with either an
adhesive or a solvent.
Monitoring of Pouches During Exposure
To monitor the pouches, the following tests were performed during the
exposure:
1. The deionized water in each of the outer bags was tested peri-
odically for pH, electrical conductivity, and for odor, e.g.
butyric acid as in the case of tests with MSW leachate.
2. The pouches containing the test liquids were removed periodically
from the water, wiped dry, inspected for possible leaks, and
weighed.
Figure 31 shows the pouches, the tray assembly for holding the
pouches, and the auxiliary equipment for monitoring the pouches.
Figure 31. Pouch and auxiliary equipment for monitoring the pouches of
polymeric membrane liners to assess permeability to water and
constituents of waste liquids. Monitoring equipment for
measuring pH and electrical conductivity of the water in the
outer bags is shown.
170
-------
During the exposure, evaporation of the water in the outer bags would
cause the water level to drop exposing the top part of the pouch to air.
The loss was replaced with additional deionized water. Also, if the
concentration of ions in the outer bag appeared to be too high due to
migration or possibly to a leak, the entire contents were replaced with
deionized water.
Dismantling of Pouch After Exposure
Most of the pouches were allowed to continue their exposure for com-
paratively long times in order to assess the effects of exposure to water
and wastes. If a leak developed in the pouch, as indicated by abrupt
changes in the monitoring data, the pouch would be withdrawn from exposure,
emptied, and the liner and liquids tested.
Dismantling of the pouches involved the following steps:
1. Weigh the pouch bag.
2. Determine pH and electrical conductivity of the water in the outer
bag.
3. Measure length and width between seams of pouch.
4. Empty pouch and weigh contents.
5. Determine pH and electrical conductivity of waste removed from
pouch.
6. Dismantle pouch at seams, leaving bottom seam intact for measure-
ment.
7. Blot the pouch dry and weigh to determine weight increase.
8. Prepare specimens for physical tests. A pattern used for dieing
out specimens in shown in Figure 32.
Tests of Exposed Membranes from Pouches
The following tests were performed on the exposed membranes:
1. Determination of percent volatiles (two hours at 105°C).
2. Determination of the percent extractables, Matrecon Test Method 2
(Matrecon, 1983, pp. 340-43).
3. Tensile in machine and transverse directions, three specimens each
direction, ASTM D412.
- Tensile strength, psi.
- Elongation at break, percent.
- Tensile set after break, percent.
- Stresses at 100 and 200% elongation, psi.
171
-------
4. Tear resistance in machine and transverse directions, two speci-
mens each direction, ASTM D624, Die C.
5. Puncture resistance, two specimens, FTMS 101B, Method 2065.
6. Hardness, Duro A (Duro D if Duro A reading is greater than 80),
ASTM D2240.
7. Seam strength, one specimen in peel (ASTM D1876, modified) and one
specimen in shear (ASTM D882, modified).
Figure 32. A pattern used for dieing out test specimens from dis-
mantled pouch made of a sheeting without fabric re-
inforcement.
Reporting of Results
The following results were reported on each pouch that was tested:
1. Properties of the unexposed membrane.
2. Properties of the membrane at the end of test, including vola-
tiles, extractables, and physical properties.
172
-------
3. Percent retention of or changes in properties during the exposure.
4. Electrical conductivity of water in outer pouch as a function of
time.
5. Weight of pouch as a function of exposure time.
6. pH of water in outer bag as a function of exposure time.
7. Measurement of amount of waste liquid in pouch at time it was
dismantled.
8. Analysis of waste in pouch, i.e. pH, electrical conductivity, and
percent total solids.
9. Calculation of water transmission rate.
EXPERIMENTAL RESULTS
Combinations of Polymeric Membranes and Waste Liquids
Seventy-one pouches made with thermoplastic and partially crystalline
membranes were tested. It was felt at the time that the feasibility and
utility of the pouch test should first be thoroughly demonstrated and that
later work could be initiated to develop designs and seaming methods for
making pouches of crosslinked membranes and thus make it applicable to all
membranes. Also, it was felt that fabric-reinforced membranes should be
avoided in the initial studies.
The combinations that were put into test are shown in Table 54. They
include 15 different membranes and 11 wastes. Pouches of elasticized
polyolefin (136), polybutylene (98), and polyvinyl chloride (19) were
filled and tested with all 11 wastes. Six different PVC membranes ranging
in thickness from 11 to 33 mils were tested and include variations in
manufacturers and in thickness of sheeting.
Monitoring of Pouches During Exposure
Pouches Containing Acidic Waste, "HNC^-HF-HOAc"--
This was the first set of pouches placed in exposure under this
project. These pouches contained a waste that was being used in several
parts of the project. Furthermore, this set was the first to complete the
entire series of tests that were planned in the basic design of the pouch
test.
As indicated above, monitoring the pouch assembly included weighing
the pouches and the measuring pH and electrical conductivity of the water
in the bags in which the pouches were immersed. In addition, the general
condition of the pouches and the waters was observed. If necessary,
deionized water was added if too much water had evaporated, and the water
was completely replaced if the concentration of ions and dissolved con-
stituents appeared to have become too high.
173
-------
TABLE 54. COMBINATIONS OF POLYMERIC MEMBRANES AND WASTES IN POUCH TESTS
Polymeric membrane
Polymer
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized poly-
olef in
Polyester elastomer
Polybutylene
Polyethylene
Low density
Polyvinyl chloride
1 iner
Number3
77 (30)
86 (22)
6R (31)
55 (35)
85 (33)
36 (22)
75 (8)
98 (8)
21 (10)
11 (30)
17 (20)
19 (22)
b9 (33)
88 (20)
93 (11)
Ac i d i c
"HN03- Alkaline
HF- "Slop "Spent
"HFL" HOAc" water" caustic"
(W-10) (W-9) (W-4) (W-2)
P45 P19 P32 P26
P18 P31 P25
P44 P17 P30A.30B P24
....
P47 P15 P28 P22
P43
...
P48
P42 P16 P29 P23
...
P20 P33 P27
P46
Brine
5%
NaCl
(W-19)
P6b
P77
P2b
P76
P4b
P7b
P78
P75
P3b
P73
P74
P5b
...
Wastes
Indus-
trial
"Basin "Lead
F" waste"
(W-16) (W-14)
P71
P70
... ...
P69 P80
... ...
P72 P81
P68
...
P66
P67 P79
... ...
... ...
...
Oily
"Slurry "Oil Pond "Weed
oil" 104" oil"
(W-15) (W-5) (W-7)
P63 P53
P56
P62
... ... ...
P85 P61 P52
... ... ...
P86 P65 P55
P60 P51
... ... ...
P57,58 P49
P87 P59 P50
... ... ...
P64 P54
Pest-
icide
"Weed
ki Her
(W-ll)
...
...
P83
P84
...
P82
...
aMatrecon liner number and thickness in mils (in parentheses).
^Results reported in Haxo et al, 1983. P - pouch number.
-------
Selected results of the monitoring are presented in Table 55 and the
data on the weight increases, pH, and electrical conductivity are presented
in Figures 33 through 35. In this set of 6 pouches, only one failed, i.e.
the polybutylene, which failed due to cracking and embrittlement caused by
exposure of the top of the pouch to light.
Note: The compartmentalized trays that contained the pouch
assemblies during exposure were kept on a table in the
laboratory and exposed to both sunlight and fluorescent
light. All pouches are now kept under cover in closed
cabinets.
The polybutylene sheeting did not contain carbon black.
These data clearly demonstrate the permeability of polymeric membranes
to water, to hydrogen ions, and possibly to other constituents. Also, they
show the difference in permeability of the membranes. These results are
discussed more fully in the following subsections.
Monitoring of Other Pouches
Sixty-five additional pouches were involved in the testing and were
monitored during the course of the project. Selected results of the
monitoring are presented in Table 56, which includes data at extended
elapsed times or at the time of failure. Included are data on the weight
gain by the pouches during the exposure and the pH and electrical conduc-
tivity of the water in the outer bags at the indicated elapsed time. In
addition, comments are included with respect to the condition of the pouch,
such as softening, stiffening, color, and the presence of oil on the
outside surface. With respect to the water in the outer bag, comment is
made on odor, color of the water, and the presence of suspended material or
oil. The pouches that contained oily wastes generally were found to swell,
soften, and exude oil on the outer surface.
Of particular interest are the results for Pouches 30A and 30B which
were fabricated of elastic!zed polyolefin and contained the highly alkaline
waste, "Slop water" (W-4). The first pouch (P30A) showed a low perme-
ability during the first year and then a much higher permeability sub-
sequently until it failed after approximately 790 days of exposure. The
pouch increased substantially in weight and the electrical conductivity of
the water in the outer bag increased to 14,000 per pmho and the pH to 12.5.
A second pouch (P30B), which replaced the first and contained the same
waste, has performed similarly, and had not failed after 1670 days. As in
the case of the first pouch, its permeability increased from a relatively
low value to a high value after about a year of exposure.
Failure of Pouches During Exposure
In spite of the testing of the pouches before filling with wastes, 13
of the 71 pouches failed prematurely, ranging from one day to 872 days.
All of the failures, except the failure of the one polybutylene pouch, were
in or at the seams. Those that failed at one and nine days were replaced.
175
-------
cr>
TABLE 55. POUCH TEST OF THERMOPLASTIC AND PARTIALLY CRYSTALLINE POLYMERIC MEMBRANES WITH ACIDIC HASTE, "HN03-IIF-HOAc"
Chlorosulfonated Polyethylene, Chlorinated Polyethylene, Elasticized Polyolefin, Polybutylene, and Polyvinyl Chloride
Monitoring of Pouches
Liner and pouch
Chlorinated polyethylene
(L-86, P19)a
Change In weight, g
pll
Electrical conductivity, pmho
Chlorosulfonated polyethylene
(L-85, P18)
Change 1n weight, g
pH
Electrical conductivity, pmho
Elastldzed polyolefln
(L-36, P17)
Change 1n weight, g
pH
Electrical conductivity, pmho
Polybutylene (L-98, P15)
Change 1n weight, g
pH
Electrical conductivity, pmho
Polyvinyl chloride (L-19, P16)
Change in weight, g
PH
Electrical conductivity, pmho
Polyvinyl chloride (L-88, P20)
Change 1n weight, g
pH
Electrical conductivity, pmho
1
-0.7
5.9
8.5
-1.61
6.6
6.3
0.01
6.4
4.1
0.02
5.5
2.7
-0.15
5.b
11.4
0.02
4.9
18.6
5
-0.52
6.0
14.8
-1.11
6.8
8.8
0.01
6.4
5.4
0.00
5.3
4.4
0.00
5.6
13.2
0.26
4.9
24.0
40
0.01
5.9
19.0
1.38
7.1
21.7
0.07
6.3
8.4
0.05
3.8
42.0
0.38
34
1.11
3.3
153
93
0.65
5.8
23.4
3.11
7.5
42.7
0.22
6.4
9.5
0.29
3.4
98
1.23
3.1
113
3.00
2.8
330
143
1.05
5.6
32.2
4.53
7.6
71
0.19
6.1
11.9
0.24
3.2
174
1.81
2.8
480
5.43
2.7
647
386
6.78
2.7
420
8.38
7.0
430
0.59
5.6
26.0
0.82
2.6
350
5.50
2.0
2000
12.93
1.8
3200
500
15.78
2.0
3550
10.18
7.8
825
0.79
5.4
230
0.82
2.8
410
7.10
2.1
2750
15.73
2.0
4500
E
552
20.28
1.6
5500
10.68
8.4
1210
0.69
5.8
115
0.82
2.6
440
7.40
1.8
3150
17.23
1.7
4900
XpOSUI'6
625
26.58
2.2
6300
12.98
7.8
1140
0.89
4.6
60
58.22
3.0
440
8.80
2.5
2900
19.43
2.3
4700
t i me ,
790
38.27
1.8
8500
17.60
7.3
1800
1.18
4.7
50
10.78
2.2
3290
23.08
4800
days
900
46.38
1.8
9900
20.77
3.0
1145
1.33
4.4
69
9.60
2.2
3900
26.16
2.0
5400
949
52.34
1.8
12,300
25.36
2.6
1710
1.42
4.2
92
13.27
2.4
3950
28.47
1.9
6700
1160
62.98
2.1
14,600
28.56
2.8
2500
1.37
4.1
92
14.70
2.2
4800
31.07
2.5
9000
1174
3.1
350
3.3
310
5.6
1
3^3
163
3.1
361
1199
65.43
2.6
900
30.86
2.8
600
1.69
4.9
8
15.35
2.8
420
32.21
2.7
680
1427
79.68
2.0
4000
39.68
2.3
1860
2.09
4.9
35
17.50
2.2
450
37.03
2.1
2570
1087
100.00
1.8
5900
56.88
2.0
3600
3.58
3.3
80
22.5
2.0
3200
45.43
1.9
4600
aL » liner number; P = pouch number.
-------
Outer liquid replaced
with Dl water
200
400
600
800
1000
Time, days
1200
1400
1600
1800
Figure 33. Monitoring of pouches that contained the highly acidic waste,
"HN03-HF-HOAc" (W-9). Weight changes of the individual
pouches P15 - P20 plotted against exposure time in days.
Outer liquid replaced
with Dl water at 1160d
200 400
600
BOO 1000 1200
Days of exposure
1400
1600
1800
Figure 34. Monitoring of pouches that contained the highly acidic waste,
"HN03-HF-HOAc" (W-9). pH of the deionized water in the outer
polybutylene bags in which pouches P15 - P20 were immersed is
plotted against exposure time in days.
177
-------
200 400 600 BOO 1000 1200 1400 1600 1800
Time, dayi
Figure 35. Monitoring of pouches that contained the highly acidic waste,
"HN03-HF-HOAc" (W-9). Electrical conductivity of the de-
ionized water in the outer polyethylene bags containing pouches
P15 - P20 is plotted against exposure time in days.
Also replaced after approximately 790 days was P30A which was made of
elasticized polyolefin and was filled with the highly alkaline waste
"Slop water" (W-4).
The incidence of seam failure appears to be predominantly among those
made of thick membranes, those seamed with solvents, and those that con-
tained "Slop water" waste. There were no seam failures among the heat-
sealed polybutylene and polyethylene pouches. Seam failures are indicative
of problems in the making of pouches; they do not reflect on the seaming by
manufacturers of the liners, either in the factory or in the field. Since
all of the heat-sealed pouches that failed were fabricated with a device
that was not intended for seaming such thick materials, these failures can
only be a reflection of the problem of using improper equipment.
Subsequently, we obtained a heat-sealing device with which we have
been more successful in preparing the seams of the thicker materials. This
latter device is also primarily in tended for making polyethylene bags; it
is semi automated and can be run at higher temperatures under controlled
pressures and times.
Note: The above heat-sealing unit is the "PAC Model 12 PI Im-
pulse Bag Sealer" purchased from Packaging Aids Corpora-
tion, San Francisco, California 94107.
178
-------
TABLE 56. MONITORING Of POUCHES
pK and Electrical Conductivity of Water- in Outer Bag and Weight Changes of Filled Pouches
Waste
Acidic - "HFL" (W-10)
Alkaline - "Slop water"
(W-4)
Alkaline - "Spent caustic"
(W-2)
Brine - 5% NaCl (W-19)
Polymer
Chlorinated polyethylene
Elasticized polyolefin
Polybutylene
Polyethylene - low density
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Elasticized polyolefin
Polybutylene
Polyvinyl chloride
Polyvinyl chloride
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Polybutylene
Polyvinyl chloride
Polyvinyl chloride
Chlorinated polyethylene
Chlorinated polyethylene
Chlorosulfonated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Polybutylene
Polyester
Polyethylene - low density
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Liner Pouch
number3 number
86 (22) P45
36 (22)
98 (8)
P44
P47
21 (10) P43
17 (20) P48
19 (22) P42
93 (11) P46
86 (22) P32
85 (33) P31
36 (22) P30A
36 (22) P30B
98 (8)
P28
19 -(22) P29
88 (20) P33
86 (22) P26
85 (33) P25
36 (22) P24
98 (8)
P22
19 (22) P23
88 (20) P27
Elapsed
time, d
1833
1833
1833
1833
1823
1833
1833
65"
2044
753b
1350
2044
872b
65b
2044
2044
2044
2044
2044
2044
Electrical Change
conductivity, in
pH umho weight
4.1
3.2
2.9
2.7
2.5
2.6
2.8
7.9
9.3
12.4
11.1
9.4
12.5
9.6
3.7
4.2
4.1
4.1
4.8
3.3
510
60
155
580
540
280
595
270
1800
10,800
5460
1950
14,700
235
102
23
73
16
660
94
11.3
0.4
0.7
1.2
4.4
3.9
9.8
2.7
36.5
213.6
227.8
16.8
152.4
...
22.4
22.5
4.2
12.6
60.3
54.9
Comments
Pouch wrinkled, coated w/brown green slime.
Pouch wrinkled.
Pouch discolored, swollen.
Leak noted at 93 d. Dismantled at 625 d.
Pouch wrinkled; blisters; odor in water.
Leaked at seam at 790 d; blisters noted.
Pouch swollen; has yellow crystals on it.
Pouch has small blisters.
Pouch very stiff; seam failed at 930 d.
Leak noted at 93 d, dismantled at 625 d.
Pouch wrinkled; coated w/brown green slime.
Pouch wrinkled.
Pouch seams wrinkled, swollen
77 (30) P6 ...
86 (22) P77
6R (31) P2
55 (3b) P76
36 (22) P4
98 (8)
75 (8)
P78
P7
21 (10) P75
11 (30) P3
17 (20
19 (22
59 (33
P73
P74
P5
316
1151
315
1151
316
928b
315
338b
310
315
1152
3.6
7.4
6.7
4.8
5.1
4.5
4.4
ili
6.4
5.4
86
585
66
34
27
71
31
22
371
16
4500
4.0
10.2
4.7
2.3
0.7
25.9
0.9
0.4
6.5
1.8
2.1
Wrinkled at seams.
Swollen.
Wrinkled.
Leak noted at 955 d.
Leak in seam at thin spotc noted at 791 d.
Continued
-------
TABLE 56. Continued
oo
o
Waste
Industrial - "Basi n F"
(W-16)
"Lead waste" (W-14)
Oily - "Slurry oil" (W-15)
Oily - "Oil Pond 104"
(W-5)
Oily - "Weed oil" (W-7)
Pesticide - "Weed killer"
(W-7)
Polymer
Chlorinated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Polybutylene
Polyethylene - low density
Polyvlnyl chloride
Polyvlnyl chloride
Elasticized polyolefin
Polybutylene
Polyvinyl chloride
Elasticized polyolefin
Polybutylene
Polyvinyl chloride
Chlorinated polyethylene
Chlorosulfonated polyethylene
Chlorosulfonated polyethylene
Elasticized polyolefin
Polybutylene
Polyethylene - low density
Polyvinyl chloride
Polyvinyl chloride
Polyvfnyl chloride
Polyvinyl chloride
Chlorinated polyethylene
Elasticized polyolefin
Polybutylene
Polyethylene - low density
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Chlorinated polyethylene
Elasticized polyolefin
Polyvlnyl chloride
Liner
number3
86 (22)
55 (35)
36 (22)
98 (8)
21 (10)
17 (20)
19 (22)
36 (71)
98 (8)
19 (22)
36 (22)
98 (8)
19 (22)
86 (22)
6R (31)
55 (35
36 (22)
98 (8)
21 (10)
17 (20)
17 (20)
19 (22)
93 (11)
86 (22)
36 (22)
98 (8)
21 (10)
17 (20)
19 (22)
93 (11)
36 (22)
98 (8)
17 (20)
Pouch
number
P71
P70
P69
P72
P68
P66
P67
P80
P81
P79
P85
P86
P87
P63
P56
P62
P61
P65
P60
P57
P58
P59
P64
P53
P52
P55
P51
P49
P50
P54
P83
P84
P82
Elapsed
time, d
38b
1641
1641
1641
1641
227°
1641
277°
1638
1638
1638
1638
1638
1485
1494
1485
1485
1485
1494
1
1485
1485
lb
1654
1654
1654
1654
1640
1654
62b
1638
1638
1638
Electrical Change
conductivity, in
pH pmho weight
4.3
8.3
7.3
7.7
6.0
4.7
8.0
5.2
7.9
4.7
3.2
3.7
4.0
4.5
5.5
5.5
3.2
3.4
3.2
2'.8
3.8
5.9
4.0
3.3
4.4
3.4
2.5
4.8
3.8
3.2
3.3
3.4
38
3600
189
230
330
33
600
11
315
46
59
56
42
190
310
320
140
130
130
...
330
49
6
420
52
39
46
448
56
54
67
46
42
1.0
10.8
2.8
4.8
10.9
7.5
29.7
-0.9
-1.4
-1.2
0.0
0.1
0.6
1.81
16.3
12.9
-1.3
-4.5
-4.3
...
-0.3
-1.2
0.0
10.3
0.3
-0.5
0.9
0.3
-0.2
2.2
0.3
0.1
-0.2
Comments
Outer bag failed at 49 d.
Pouch wrinkled at edges.
Pouch smooth; leak in seam at 727 d.
Pouch slightly wrinkled.
Pouch smooth; leak in seam at 726 d.
...
...
Pouch wrinkled; oil on surface; stained.
Pouch sticky; oil on surface; stained.
Pouch wrinkled; oil on surfaced.
Pouch flat.
Pouch swollen, blistered.
Pouch flat, puckered.
Pouch flat, possible seam leak.
Oil on pouch outer surface.
Oil on pouch outer surface.
Failed at 1 d.
...
Pouch puckered and stiff.
Seam leaked at 9 d.
Brown sediment in pouch bottom.
Brown sediment in pouch bottom.
Pouch has small blisters.
Pouch has small blisters.
Seam open, pouch flat; noted at 78 d.
White rubbery sediment in pouch.
aMatrecon liner serial number. Thickness, in mils, in parentheses.
^Leak detected in bag during next monitoring.
cThinness probably related to overheating during heat-sealing.
pouch was viewed under ultraviolet light and the oil flouresced.
-------
Other Observations--
Many of the pouches that contained oily wastes appeared to have
been permeated by the oily constituents. The outsides of the pouches
were tacky and oily and, in some cases, the water in the outer bag had
a strong oily odor. It is apparent that some of the organic wastes
have permeated the pouch walls and dissolved in the water in the outer
bags. However, direct analyses of these waters were not made.
Dissecting of Pouches Containing the "HN03-HF-HOAc" Acidic Waste
Condition of the Pouch Assemblies
As indicated above, the pouch (P15) made of polybutylene failed
at 609 days and was removed and tested at 625 days. Five of the original
pouches survived to 1887 days of exposure. These were dissected so that
the pouches and the contents of the pouches could be weighed, the contents
analyzed, and the properties of the pouch walls measured.
All of the pouches either had retained approximately their original
flexibility or had swollen and softened during the exposure period. The
water in the outer bags had a chemical or acrid odor indicating migration
of constituents from the waste liquid in the pouches to water in the outer
bag.
The CPE pouch (P19) appeared to be in good shape at the time of
dismantling, although the seams were relatively easy to pull apart. The
surface on the inside of the pouch was somewhat pitted. The membrane had
obviously swollen.
The CSPE pouch (P18) had blistered badly on one side. This sheeting
was not fabric-reinforced. The liquid contents of the blisters were
removed with a hypodermic needle and analyzed for pH and electrical conduc-
tivity. The pH of the liquid was 1.35 and the electrical conductivity of
a 1:1 dilution with deionized water was 12,400 ymho. The waste fluid
obviously permeated into the sheeting which delaminated relatively easily
in the area of the blisters when pulled by hand.
The pouch made of elasticized polyolefin (P17) retained its original
condition well during exposure. It appeared to have changed little during
the 1887 days of exposure.
The pouch made of polybutylene (P15), which had failed at 609 days and
was dismantled at 625 days, was badly cracked at the upper seam due to
light degradation. The portion of the pouch that was below the water level
of the outer bag appeared to have retained its flexibility and original
properties.
Pouch 16, made of PVC liner No. 19, was flexible but the inside was
sticky. Also, the seams which, had been made with a solvent seal of 50:50
tetrahydrofuran:trichloroethane, were easy to peel apart.
181
-------
Pouch 20, made of PVC liner No. 88, had stiffened somewhat during
exposure. The outside surface had become rough and discolored compared
with the unexposed material. The inside was considerably more discolored
and pitted, indicating some interaction between the membrane and the waste
liquid.
Weights--
The various weights of the pouches and the contents of the pouches
are presented in Table 57. These data confirm the monitoring data; they
show substantial increases in the contents of the pouches of CPE (P19),
CSPE (P18), PVC (P16), and PVC (P20), further demonstrating the movement
of water from the outer bag into the pouch due to the concentration dif-
ferences between the liquids on the two sides of the membrane.
The pH and electrical conductivity measurements of the water in the
outer bags also show the movement of the hydrogen ions out of the pouches
into the water in which the pouches were immersed. The lower conductivity
and higher pH of the waste removed from the pouches at the end of the
exposure period when compared with the waste placed in the pouches at the
beginning further confirm this. The elasticized polyolefin pouch wall had
a particularly low permeability to water and the dissolved consitituents of
the waste.
Analysis of the Contents of the Pouches and of the Outer Bags
On opening the pouches the contents were collected, weighed, and
tested for pH and electrical conductivity. The results, presented in Table
57, show a substantial increase in the volume and a significant decrease in
the electrical conductivity of the contents, indicating a dilution by the
water that had entered through the pouch walls. Calculations of the
transmission of the water through the pouch walls were made and are re-
ported in Table 57. The calculations show the chlorinated polyethylene to
be the most permeable of the group and the elasticized polyolefin the
least.
These transmission values correlate well with the values calculated
from the weight increases of the pouches during the exposure. However, the
fact that part of the increases in weight are a result of the absorption of
water by the pouch walls requires that the earlier values be corrected.
Although the polybutylene bag failed prematurely, the transmission value
based on the weight gains were low.
Physical Properties of the Pouch Walls--
After their contents were removed, the pouches were cut, washed, and
tested as described in the basic pouch test procedure. These tests in-
cluded analytical properties, i.e. volatiles and extractables, and physical
properties, i.e. tensile, tear, puncture strength, hardness, and seam
strength. Results of these tests are presented in Table 58, and the
percent retentions of properties are presented in Table 59.
182
-------
TABLE 57. POUCH TEST OF THERMOPLASTIC AND PARTIALLY CRYSTALLINE POLYMERIC
MEMBRANES WITH ACIDIC WASTE, "HN03-HF-HOAc" (W-9)
Chlorosulfonated Polyethylene, Chlorinated Polyethylene, Elasticlzed
Polyolefin, Polybutylene, and Polyvinyl Chloride Data on Pouch and
Waste Before and After Dismantling
Polymer
Matrecon liner serial number
Liner thickness, mil
Pouch number
Number of days exposed
Chlorinated
polyethylene
86
22
P19
1887
Chlorosulfonated
polyethylene
85
33
P18
1887
Elasticized
polyolefin
36
22
P17
1887
Polybu-
tylene
98
8
P15
609a
Polyvinyl
chloride
19 88
22 20
P16 P20
1887 1887
.24
.82
122.98
114.16
33.24
34.09
35.18
1.94
1.09
5.8
176.60
199.10
22.50
142.51
163.54
21.03
0.90
463
2.0
4,800
3,200
0.252
31.68
33.45
43.14
11.46
9.69
36.2
189.47
234.90
45.43
156.02
191.86
35.84
1.05
Effective area of pouch (seam-
to-seam) of exposed pouch, m2 0.0431 0.0484 0.0446 ... 0.0443 0.0523
Weight of empty pouch
Unexposed, a 39.17 59.03 27.32
Conditioned", g 57.44 79.46 26.70
After exposure, g 53.45 87.49 28.35
Change from unexposed, g 14.28 28.46 1.03
Change from conditioned, g -3.99 8.03 1.65
Change from unexposed, % 36.5 51.8 3.8
Weight of filled pouch
At beginning of exposure, g 250.22 261.93 128.31
After exposure, g 350.22 318.80 131.89
Change in weight, g 100.00 58.87 3.58
Waste contents of pouch
Weight at beginning of exposure, g 192.79 182.47 101.61
Weight after exposure, g 291.49 229.04 103.01
Change in weight, g 98.70 46.57 1.40
pH after exposure0 1.10 1.00 0.95
Electrical conductivity11, after
exposure, umho 110,000 170,000 170,000
Liquid in outer bag
Volume at conclusion of test, mL 375 395 520
pH at conclusionn of test 1.80 1.95 3.25 3.0
Electrical conductivity
Before water change*, vmko 14,600 2,500 92
At conclusion of test, ymho 5,900 3,600 86 440
Water transmission through pouch wall,
g/m2/day 1.213 0.510 0.017 ._._.
aPouch failed due to cracking and embrittlement at upper seam caused by light degradation. Film was unpigmented,
i.e. it contained no carbon black to absorb ultraviolet light.
bEmpty pouches conditioned for two weeks in water at 70°C before waste added. Water added to CPE pouch (P19)
after one week to prevent sides from sticking together.
cpH at beginning of test = 0.9.
dElectrical conductivity of waste at beginning of test = 200,000 pmho.
eThe volume of liquid in outer bag varied in course of exposure due to evaporation. Deionized water was added
periodically to cover the pouches.
fOuter liquid replaced with deionized water after 1169 days of exposure.
170,000 140,000
400
1.85
9,000
4,600
0.363
183
-------
00
-pi
TABLE 58. POUCH TEST OF THERMOPLASTIC AND PARTIALLY CRYSTALLINE POLYMERIC MEMBRANES WITH ACIDIC WASTE, "HN03-HF-HOAc" (W-9)
Chlorosulfonated Polyethylene, Chlorinated Polyethylene, Elasticized Polyolefin, Polybutylene, and Polyvinyl Chloride
Properties of Membranes after Exposure
Polymer
Matrecon liner sarial number
Nominal thickness, mil
Exposure time, days
Analytical properties
Volatiles , %
Extractables, %
Physical properties
Average thickness, mil
Tensile at break, psi
Elongation at break, %
Set after break, %
S-100, psi
S-200, psi
Tear strength, ppi
Puncture strength
Thickness, mil
Stress, Ib
Elongation, in.
Hardness (durometer) ,
5-second reading
Seam strength
Bonding system
In shear, ppi
Locus of failure13
In peel , ppi
Locus of failure*5
Direction
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Chlorinated
polyethylene
86
22
1887
46.53
...
35.9
760
460
265
315
85
45
405
160
625
270
85
60
39.0
11.4
0.70
45A
Heat
11.7
LS
2.2
LS
Chlorosulfonated
polyethylene
85
31
1887
34.39
41.6
860
935
180
185
20
30
425
470
...
80
40.0
42.3
0.73
54A
Adhesi ve
...
...
Elasticized
polyol ef in
36
22
1884
8.26
7.73
23.1
2455
1985
680
620
455
375
895
845
975
925
380
350
24.4
36.4
1.22
85A
28D
Heat
...
20.6
SE
Polybu-
tylene
98
8
609
4.70
10
5610
5690
350
390
200
235
2830
2790
3770
3420
« . .
. . .
Heat
...
...
Poly vinyl
chl oride
19
22
1887
12.33
38.58
22.6
2290
2120
345
355
80
90
1285
1230
1705
1580
290
295
23.8
38.4
0.84
72A
Solvent3
28.0
SE
6.0
LS
88
20
1887
30.35
34.12
26.1
1865
1600
240
250
50
45
1255
1130
1690
1470
265
210
26.5
20.4
0.40
74A
Heat
25.8
SE
11.6
LS
a50:50 tetrahydrofuran:trichloroethane mixture.
t>LS = Failed at the bond between the adhered liner surfaces. SE = failed at the seam edge.
-------
CO
en
TABLE 59. POUCH TEST OF THERMOPLASTIC AND PARTIALLY CRYSTALLINE POLYMERIC MEMBRANES WITH ACIDIC WASTE,
Chlorosulfonated Polyethylene, Chlorinated Polyethylene, Elasticized Polyolefin, Polybutylene, and
Retention of Original Values
"HN03-HF-HOAc" (W-9)
Polyvinyl Chloride
Polymer
Liner number
Nominal thickness, mil
Exposure time, days
Analytical properties
Volatiles
Unexposed, %
Exposed, %
Extractables
Unexposed, %
Exposed, %
Physical properties
Thickness, % of original
Tensile at break, % ret.
Elongation after break, % ret.
Set after break, % ret.
S-100, % ret.
S-200, % ret.
Tear strength, % ret.
Puncture strength
Stress, % ret.
Elongation, % ret.
Hardness (durometer), change
in 5-second reading
Chlorinated
polyethylene
86
22
1887
Direction
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
0.05
46.53
6.02
167
41
30
75
53
41
19
47
58
52
67
45
34
55
0.70
-22A
Chlorosulfonated
polyethylene
85
31
1887
0.92
34.39
8.22
126
37
45
69
57
12
16
37
63
29
88
0.73
-25A
Elasticized
polyolefin
36
22
1884
0.15
8.26
5.50
7.73
100
93
78
101
95
99
87
102
98
100
96
98
95
138
1.22
+2A
Polybu- Poly vinyl
tylene chloride
98 19
8 22
609 1887
0.05
12.33
4.42 38.91
4.70 38.58
108
82
94
105
104
82
86
112
116
93
99
98
107
160
0.84
OA
88
20
1887
0.17
30.35
33.46
34.12
131
55
55
74
75
49
45
67
71
65
67
57
45
71
0.40
-6A
-------
Comparison Between the Pouch Test and the Immersion Test--
The increases in weight of the pouch walls relate to the weight gains
obtained in immersion-type tests. However, there may be significant
differences as shown in Table 60 which compares the weight increases of the
pouch walls with the weight increases of the same or similar membranes
in immersion tests. Most of the weight gains in the pouch test were higher
than those in the immersion tests with acidic waste, "HNC^-HF-HOAc" and
deionied water. However, this may reflect: (1) the longer exposure time,
1887 days vs 751 days, and (2) the absorption of deionized water which is
generally greater than that of an aqueous solution containing dissolved
salts.
TABLE 60. WEIGHT CHANGE OF MEMBRANES DURING EXPOSURE
Comparison of Pouch and Immersion Tests
Pouch test3
Immersion test
Liner
Polymer
Chlorinated
polyethylene
Chlorosulf onated
polyethylene
Number^
77 (30)
86 (22)
55 (35)
85 (33)
Time,
days
*
1887
1887
Wei ght
change, %
36.4
48.2
Time
days
751
751
Wei ght
change in
waste0, %
19.9
*
10.9
Wei ght
Change in
deionized
water, %
12.4
18.9
Elasticized
polyolefin
Polyvinyl
36 (22) 1887
3.8
751
7.57
0.6
chlori de
11 (33)
19 (22)
59 (33)
88 (20)
1887
1887
*
5.8
36.2
751
*
751
751
22.1
-6.12
28.2
-1.6
-0.5
-0.1
aPouches contained acidic waste "HN03-HF-HOAc" and were immersed in de-
ionized water. Pouches included seams.
^Matrecon liner number and thickness, in mils, in parentheses.
cAcidic waste "HN03-HF-HOAc."
In Table 61, the extractables of the pouch walls are compared with the
extractables of the same or similar respective membranes in the immersion
test with the acidic waste, "HN03-HF-HOAc." In both cases, the changes
during exposure were small, except in the case of PVC liner (59) which
decreased in extractables significantly during exposure (23.25% vs original
of 35.87%).
186
-------
TABLE 61. COMPARISON OF EXTRACTABLES OF EXPOSED MEMBRANES AFTER POUCH AND
IMMERSION TESTS WITH ACIDIC WASTE, "HN03-HF-HOAc" (W-9)
Liner
Polymer
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized
polyolefin
Poly vinyl
chloride
Number3
77 (30)
86 (22)
55 (35)
85 (33)
36 (22)
11 (33)
19 (22)
59 (33)
88 (20)
Original
value, %
9.13
6.02
4.08
5.50
33.90
38.91
35.86
34.46
Pouch test
Exposure Extract-
time, d ables, %
1887
1887 10.34
1887
1887 33 '.46
1887 34.12
Immersion test
Exposure
time, d
751
751
751
751
751
751
Extract-
ables, %
12.04
3.96
6.22
32.25
23*.25
33.20
aMatrecon liner number and thickness, in mils, in parentheses.
In Table 62 the results on stress at 100% elongation (S-100) of the
membranes after exposure in the pouch test are compared with those on the
same or similar membranes from the immersion test with the acidic waste,
"HN03-HF-HQAc." The results of this comparison are not clear because of
the variation in the response of the individual liners to the exposure.
However, in the two cases where the same sheeting was used, the values were
comparable, even though the time periods were greatly different.
Permeability
The primary purpose of this test was to assess the permeability of the
liner materials in a condition that simulates some of the conditions in a
pond. The results indicate the extent of migration of several waste
constituents simultaneously, i.e. water, dissolved ions, both cations and
anions, and organics.
Water--
The clearest results in the pouch test with the acidic waste, "HN03-
HF-HOAc," were those regarding the transmission of water. Deionized water
in the outer bag was transmitted into the concentrated waste inside the
pouch by osmosis resulting from the large concentration gradient across the
membrane. Such results indicate that a pond lined with a membrane liner
placed in a moist, perhaps saturated, environment in which the water is
relatively pure would receive water from the environment outside the pond.
This would be true even if there were no holes or breaks in the liner
187
-------
TABLE 62. COMPARISON OF THE RETENTION OF STRESS AT 100 PERCENT
ELONGATION OF MEMBRANES EXPOSED TO ACIDIC WASTE
"HN03-HF-HOAc" IN POUCH AND IMMERSION TESTS
Original Pouch test Immersion test
Liner value, Exposure Reten- Exposure Reten-
Polymer Number* psi time, d tion, % time, d tion, %
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized
polyolefin
Poly vinyl
77 (30)
86 (22)
100 (36)
55 (35)
85 (33)
900
575
617
880
950
1887
53
36 (22) 923
1887
1887
50
100
751
751
751
751
129
45
71
93
chloride
11
19
59
88
(33)
(22)
(33)
(20)
1420
1330
995
1735
1887
1887
114
69
751
751
751
93
252
70
aMatrecon liner number and thickness, in mils, in parentheses.
itself. However, water is not a polluting constituent. In the diffusion
process, it migrates through the liner as an independent molecular species.
Permeability of Ions--
In the case of pouches and ponds, concentrated solutions are on one
side and the purer water with fewer dissolved constituents is on the other.
In such an environment, the concentration difference results in a gradient
or driving force which causes the dissolved constituents to move from the
concentrated solutions into the less concentrated. Thus, there can be a
movement of ions, such as hydrogen ions, hydroxyl ions, and other cations
and anions, out of the pouch or the pond into the ground. This occurs in
the case of the pouches; in the tests with the highly acidic waste "HN03-
HF-HOAc," the hydrogen ions in the pouch migrated through the walls and the
pH of the outer solution dropped due to increased hydrogen ion concentra-
tion, and the electrical conductivity increased. The difference between
the permeabilities of the different sheetings is quite apparent.
Organics
Several of the wastes were oily, resulting in a film of oil being
formed on the outside of the pouches and, since the oils themselves were
not soluble in water, they tended to remain on the surface of the pouch and
188
-------
stop further movement of oils through the wall. If the oils had been
soluble in the water, the concentration of the oil on the downstream side
of the membrane would have been lower and migration of the oil would have
continued.
DISCUSSION
Comparison of Permeability Results
In the pouch test with the acidic waste and the six different poly-
meric membrane liners, relative permeability data were obtained on two
constituents, i.e. water and dissolved ions. These are reflected by the
weight increases of the pouches, the increases in electrical conductivity,
and the changes in pH during exposure. These results were presented in
Figures 33 through 35.
In Table 63 the relative ordering of the permeabilities among the
six polymeric membranes is presented for water and hydrogen ions as mea-
sured by pH and electrical conductivity. In the same table the relative
permeabilities as measured by moisture vapor transmission in the E-96 test
are also presented.
The pouch test results indicate that the elasticized polyolefin has
the lowest permeability to water and to the hydrogen ions and the poly-
butylene the second lowest. The highest permeabilities were shown by the
CPE and the two PVC's. The pouch of CPE showed a low permeability during
the early stages, comparable to the values indicated by the moisture vapor
transmission; however, after a year of exposure, during which the changes
in weight of the pouch, the electrical conductivity, and pH were small,
significant increases in weight and conductivity took place. These effects
would indicate that the permeability of the CPE increased, probably due to
high water absorption. It is also possible that pinholes may have devel-
oped in the membrane during the exposure period as the inside of the pouch
had a pitted appearance. There was no apparent failure at the seams that
would have caused a very abrupt increase in conductivity such as was
encountered with the polybutylene.
There was also an indication that the relative order of permeability
is not the same for all of the constitutents of a waste. In addition, it
would appear that maintaining a membrane in a moist condition is necessary
for assessing the long-term permeability of membranes which may slowly
become affected by the waste liquid. The moisture vapor transmission test
maintains one side of a membrane quite dry at 50% humidity, whereas the
other side is maintained at 100%. Even under these conditions, some
increases in moisture vapor transmission have been observed in long-term
tests.
189
-------
TABLE 63. RELATIVE ORDERS QF PERMEATION OF POLYMERIC MEMBRANES
TO WATER AND HYDROGEN IONS, IN POUCH TEST WITH ACIDIC WASTE,
"HN03-HF-HOAc" (W-9), AND TO MOISTURE VAPOR IN ASTM E96 TEST
Pouch status at 1887 days
Li ner
Polymer
Number^ Water0
Electrical
conduct!vi
Moisture
vapor trans-
mission, E96
g/m2 d Order
Chiori nated
polyethylene
Chloro-
sulfonated
polyethylene
Elastlcized
polyolefin
Polybutylene
86 (22)
85 (33)
36 (22)
98 (8)
1
If
0.643
0.438
1 0.142
Polyvi nyl
chl oride
19 (22)
88 (20)
2
3
4
5
4
3
2.78
2.94
4
5
aOrder of increasing permeation through polymeric membranes in test,
1 = Least permeable and 6 = most permeable.
^Matrecon liner number and thickness, in mils, in parentheses.
cBased on change in weight of filled pouch for 400 d exposure and change
in weight of contents of pouch for 1800 d exposure.
dElectrical conductivity of water in outer bags.
epH of water in outer bags.
^Extrapolated.
Comparison of Retention of Physical Properties in
Pouch and Immersion Tests
The retention of properties of the liners in the pouch and immersion
tests appear to be comparable as shown in Table 62. Addition information
of this type will become available when the remaining pouches are removed
from exposure, measured, dissected, and tested.
Expansion of Pouch Test Method to all Polymeric Membranes
The pouch method for assessing the permeability of membranes over
long periods of time and of the durability of these materials in contact
with wastes appears to be a highly feasible method of assessing the mem-
branes, though extended exposures may be required. This conclusion is
based on the results with the more flexible sheetings of thermoplastic and
partially crystalline materials. An expansion of this test method to
crosslinked polymers and elastomers, to thicker and more rigid sheetings,
190
-------
and to fabric-reinforced materials appears to be desirable. To achieve
good seams in the pouches may require the development of special adhesives
and possibly new pouch designs which can accommodate the more rigid mate-
rials, e.g. 100 mil HOPE. It is desirable, of course, to use the com-
mercial sheetings to fabricate these pouches and not to depend upon a
molded container.
191
-------
SECTION 10
PYROLYSIS ANALYSIS OF POLYMERIC MEMBRANE LINERS
As has been pointed out in Section 5, the composition of liners, even
those based on a given polymer, varies from manufacturer to manufacturer.
Differences can be used to identify or fingerprint a compound. Pyrolysis
is a method by which such an analysis can be made; it is the process by
which materials break down and lose mass on exposure to heat. This tech-
nique is useful in the determination of the composition of polymeric
compounds because individual components of a mixture may be pyrolyzed
selectively by proper control of the experimental conditions.
In the pyrolysis procedure, the specimen is weighed at specified
points throughout the experiment. The most sophisticated mode of pyrolysis
in current use is thermogravimetric analysis (TGA). This analysis provides
a continuous record of the sample weight throughout the procedure and is
ideally suited to applications where the kinetics of degradation are
important. The use of TGA for the analysis of polymeric membrane liners
has been described and test results presented (Haxo, 1983).
Membrane liners are generally compounded from four classes of mate-
rials:
1. Organic polymers, e.g. polyethylene, polyvinyl chloride.
2. Monomeric organic chemicals, e.g. plasticizers, antioxidants.
3. Inorganic fillers, e.g. clays, silicates, silica, and talc.
4. Carbon black.
The weight percent of each of these components in a given membrane liner
can be accurately determined by the combination of pyrolysis with solvent
extraction.
Pyrolysis under a nitrogen atmosphere will result in the loss of the
monomeric organic additives and of a known proportion (experimentally
determined) of the organic polymers. The carbon black and filler will
not be affected. Further pyrolysis under air or oxygen will result in the
loss of the carbon black and any carbonaceous residue remaining from the
polymer. The filler will still generally be unaffected. Solvent extrac-
tion (Appendix M) of another specimen of the membrane gives a specific de-
termination of the monomeric organic content, e.g. plasticizer or oil, and
192
-------
allows a full determination of the liner composition. Table 64 outlines
the weight losses occurring under each experimental condition.
TABLE 64. LINER WEIGHT LOSSES OCCURING ON PYROLYSIS AND EXTRACTION
Degree of loss through pyrolysis Solvent
Under N£ Under D£ extraction
Organic polymers
Monomeric organic
additives
Carbon black
Inorganic f il ler
Partial to complete
Compl ete
None
None
Complete
Complete
Compl ete
None
None
Compl ete
None
None
As indicated in the preceding paragraph and in Table 64, N^ pyrolysis
of a liner may result in only partial loss of the polymeric component.
This is especially true of polymers containing chlorine, other halogens, or
nitrogen. These materials will not smoothly depolymerize and volatilize
under nitrogen, but tend to leave behind a carbonaceous residue which
subsequently is lost with the carbon black under oxygen. In order to
accurately determine the liner composition, it is necessary to know the
percent weight of carbonaceous residue found for each polymer in question.
Table 65 summarizes data obtained from the literature and determined at
Matrecon for some common membrane lining materials:
TABLE 65. CARBONACEOUS RESIDUE FOLLOWING
PYROLYSIS UNDER N2 AT 550°C
Polymer
Neoprene
Polyvinyl chloride
Chi orosul fonated polyethylene
Butyl rubber
Wei ght,
Matrecon
13.9
4.9
0.5
%
Wakea
13.9
5.9
*
0.10
aSource: Wake, 1969, p 141.
Other corrections may be also applied for volatiles loss from fillers
and/or carbon black and for C02 loss from a carbonate filler, e.g CaC03.
These are relatively minor and are detailed in Chapter 8 of Wake (1969).
The experimental procedure used at Matrecon is outlined in Appendix
N. Table 66 presents the membrane liner composition data obtained at
Matrecon using the pyrolysis method. Ash results obtained in pyrolysis
tests which use small specimens are compared with those obtained in the
standard ASTM Test D297.
193
-------
TABLE 66. ANALYSES OF POLYMERIC LINER MEMBRANES BY PYROLYSIS
Data are in Percent by Weight
UD
Liner
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Ethylene propylene
rubber
Neoprene
Number3
22
44
57R
12
77
86
99
6R
55
8
16
26
36
83R
91
9
43
82
Polyester elastomer 75
Polyvinyl chloride
11
17
59
88
93
96
97A
Extractables
+ polymer
57.9
59.7
53.0
82.9
81.6
76.9
59.2
47.3
44.6
55.9
64.7
57.1
94.6
53. 5C
58.1
59.2
59.2
59.7
95.6
86.2
87.1
93.4
95.2
90.1
87.0
89.0
Polymer
47.9
46.6
75.4
72.5
70.9
43.6
40.4
32.5
35. 3C
34.4
49.1
45.5
46.3
92.9
52.3
49.9
57.5
61.7
57.8
52.9
54.6
Carbon
black
21.5
37.8
27.4
2.2
2.8
6.2
37.5
45.9
53.0
37.8
31.1
37.0
5.4
47. lc
35.7
30.3
29.6
27.6
6.4
6.3
4.8
2.2
2.8
6.4
6.7
4.4
Ash
Pyrolysis
20.6
2.6
19.6
14.9
15.6
17.0
3.2
6.9
2.4
6.4
4.3
6.0
0.0
0.0C
6.2
10.5
11.1
12.7
-1.8
7.5
8.2
9.3
2.7
3.6
6.4
6.7
ASTM D297
4.3
23.4
14.4
12.6
*
3.3
3.3
6.4
7.6
0.9
0.3
7.3
12.2
13.2
0.4
6.2
5.8
6.9
2.8
5.6
5.8
Extractables'3
11.8
6.4
7.5
9.1
6.0
3.8
4.1
23.4
18.2
23.6
10.2
13.7
13.4
2.7
33.9
37.3
35.9
33.5
32.3
34.1
34.4
aMatrecon liner number; R = fabric-reinforced.
^Matrecon Test Method 2, Appendix M.
cValue based on one determination. All others based on duplicates.
-------
REFERENCES
Burke Rubber Co. 1973-1979. Product Installation Information, San Jose,
California.
Dallaire, Gene. 1975. Tougher Pollution Laws Spur Use of Impermeable
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Dedrick, A. R. 1980. The History of Butyl Rubber Membranes for Water
Conservation in Agriculture. In: The Role of Rubber in Water Con-
servation and Pollution Control. Henry C. Remsberg Memorial Sym-
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Society John Gifford Memorial Library and Information Center, Akron,
Ohio. pp. II-l - 11-13.
Du Pont. 1963. The Language of Rubber. E. I. du Pont de Nemours & Co.
(Inc.), Elastomer Chemicals Department, Wilmington, Delaware. 71
pp.
Du Pont. 1973. Pond, Pit Reservoir Liners of Du Pont Hypalon. Brochure
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Dept. Wilmington, Delaware. 15 pp.
EPA. 1974. Report to Congress: Disposal of Hazardous Waste. SW-115.
U.S. Environmental Protection Agency, Washington, D.C. 110 pp.
Ganje, T. J. and A. L. Page. 1974. Rapid Acid Dissolution of Plant Tissue
for Cadmium Determination by Atomic Absorption Spectrophotometry.
At. Absorpt. Newsl. 13: 131-134.
Geswein, A. J. 1975. Liners for Land Disposal Sites: An Assessment.
EPA/530/SW-137, U.S. Environmental Protection Agency, Washington,
D.C. 66 pp.
Haxo, H. E. 1976. Assessing Synthetic and Admixed Materials for Lining
Landfills. In: Gas and Leachate from Landfills - Formulation, Col-
lection and Treatment. EPA-600/9-76-004, U.S. Environmental Pro-
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Haxo, H. E. 1976. Evaluation of Selected Liners When Exposed to Hazardous
Wastes. Proc. Hazardous Waste Research Symposium. Residual Manage-
ment by Land Disposal. EPA-600/9-76-015, U.S. Environmental Pro-
tection Agency, Cincinnati, Ohio. pp. 102-111.
195
-------
Haxo, H. E. 1978. Interaction of Selected Lining Materials with Various
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Symposium: Land Disposal of Hazardous Wastes. EPA-600/9-78-016,
U.S. Environmental Protection Agency, Cincinnati, Ohio. NTIS
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80-175-086.
Haxo, H. E. 19806. Laboratory Evaluation of Flexible Membrane Liners
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Haxo, H. E. 1981. Testing of Materials for Use in Lining Waste Disposal
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81-173-882.
Haxo, H. E. 1982. Effect on Liner Materials of Long-Term Exposure in
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196
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198
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APPENDIX A
SUMMARY LIST OF THE EXPOSURES OF FLEXIBLE POLYMERIC MEMBRANE LINERS TO HAZARDOUS WASTES3
Polymer
Butyl rubber
CPE
CSPE
ELPO
EPDM
HDPE
LDPE
Neoprene
Polybutylene
Polyester
Polypropylene
PVC
Liner
number
44
67R
77
86
100
6R
55
85
125R
36
8
26
83R
91
105
21
108
43
82
90
98
75
106
11
17
19
59
88
89
92
93
Type of
compound
XL
XL
TP
TP
XL
TP
TP
TP
TP
CX
XL
XL
TP
XL
CX
CX
CX
XL
XL
XL
CX
CX
CX
TP
TP
TP
TP
TP
TP
TP
TP
Nominal
thickness, Primary
mils cells
62
34 2,9,11,14
30 2,5.9,11,14
22
36
31 2,5,9,11,14
35
33
36 17.18
20 2,4,5,9,10,11,
14.15,17,18,21
62
26 2,9,11,14
39
37
32
10
31
34 2,5,11,14,16,
17
60
37
8
7 2,5,9,11.14
15
33
30
20
22
30 2,4,5,9,10,
11,14,15
20
11
20 18,21
11
Weather
Immersion Tub Rack Pouches
2,4,5,7,9,10,11 ... x
14,15.18,19,20
4 x
2,4.5,7,9,10,11 2 x 19
14,15,18,19,20
2,5,7,9,10,19
2,4,5,7,10,11,14
15.16,18.19.20
2,4,5,7,9,10,11 4,9 x 5,19
14,15.18.19.20
2,4,5,7,9,10,11 5,16,19
14,15,19,20
2,4,9
2,4,5,7,9,10,11 5,2 x 2,4,5,7,9.10,
14,15,18.19,20 11,14.16.16.19
2,9 x
... ... x ...
2,4,5.7,9.10,11
14,15,18,19.20
2,4,5,7,9,10,11
14,15.18,19,20
2,4,5,7,9,10,11
14,15,16,18,19,20
5,7,10,16,19
2,4,5,7,9,10,11
14,15,16,18,19,20
... ... x ...
5 x
2,4,5,7,9,10,11
14,15.18,19.20
2,4,5,7,10,11
14,15,16.19
2,4,5,7,9,10,11 5 x
14,15,18,19,20
2,4.5,7,9,10 11
14, 15, 16, 18, 19, ?0
2,4,5,7,9,10,11 9 x
14,15,18,19,20
5,7,10,16,19
2,5,7,9,10,11
14,15,16,19
2,4,5,7,9,10,11 5 x 19
14,15,18,19.20
2,4,5,7,9,10,11 2,7,9
14,15,18,19
20
18
7,5
Exposed
to MSW
leachateb
x
x
x
...
x
X
X
...
...
X
X
x
x
...
X
x
X
x
X
x
x
X
X
X
x
x
x
X
aCode for wastes 1n exposure:
2 = spent caustic; 4 slopwater;
14 = Pb waste; 15 - aromatic oil w;
20 = 0.1X tributyl phosphate; 21 =
DHaxo et al, 1982, Table 42, page 125.
5 = 01! pond 104; 7 = weed oil; 9 - nitric acid waste; 10 - HF waste; 11 pesticide;
ste; 16 = Basin F; 17 = Well 118; 18 = deionized water; 19 = 5% NaCl solution;
50% Well 118/50* deionized water.
199
-------
APPENDIX B
PROCEDURE
for
ANALYSIS AND CHARACTERIZATION OF WASTE LIQUIDS AND SLUDGES
Used by
THE SANITARY ENGINEERING RESEARCH LABORATORY,
UNIVERSITY OF CALIFORNIA, BERKELEY, CA
in the
Analysis of Wastes
200
-------
ANALYSIS AND CHARACTERIZATION OF WASTE LIQUIDS AND SLUDGES
Characterization Scheme
MULTIPHASE SAMPLES
PHASE I. AQUEOUS INSOLUBLE
ORGANIC LIQUID
PHASE
A. Flash point
B. Distillate at 95°C
C. Viscosity
D. ASTM D2007-73
- Asphaltenes
- Polar compounds
- Saturated hydro-
carbons
- Aromatics
E. IR analysis
(Chloroform extraction)
F. Water content
PHASE II. AQUEOUS PHASE
A. Total solids and
volatile solids
B. pH, Total acuity
and alkalinity
C. Water soluble vola-
tile organics
D. Oil and grease
E. Lead analysis (AA)
F. IR analysis of organics
(Chloroform extraction)
PHASE III. SOLID PHASE
A. Flammabi lity
B. Percent inorganic
and percent organic
(ashing)
C. Water extract
Note: 1. Separate a multiphase sample into Phases I, II, or III (as needed) using cen-
trifugation or filtration. Report percent by weight of each phase present.
2. References to sources of test methods see Table 1.
201
-------
PHASE I. AQUEOUS INSOLUBLE ORGANIC LIQUID PHASE
A. FLASH POINT
Determine flash point per ASTM D93-62 (closed cup) for fuel oils and
viscous materials or ASTM D92 (open cup) for volatile flammable materi-
als having flash point between 0-175°F.
B. DISTILLATE AT 95°C
If the organic phase is 10% by volume or higher, perform steam dis-
tillation up 95°C vapor temperature, noting volume of distillate. Multiply
volume of distillate by 0.8 and report as percent by weight of organics
boiling below 95°C. Record weight of organics boiling above 95°C as
percent by weight. Obtain this value from organic phase remaining in
distillation flask using volume times 0.8 to obtain weight percent.
C. VISCOSITY
Determine viscosity per ASTM D2983 at 10°C, 20°C, and 30°C.
D. ORGANIC GROUPS
Determine organic group content per ASTM D2007-69 chromatographic
method. Report in percent by weight.
E. IR ANALYSIS
Chloroform extract.
F. WATER CONTENT OF PHASE I BY A TOLUENE AZEOTROPE METHOD
(KOLTHOFF & SANDELL, 1943)
Weigh in a 250 mL stoppered round bottom distillation flask about
100 mL of PHASE I. Add glass beads and about 100 mL of toluene and swirl
vigorously. Reflux the mixture for 30 minutes using a Henion design dis-
tillation head with finger type condenser. Collect the distillate at
85+2°C in a graduated separatory funnel. Shake the distillate and
allow the phases to separate. Repeat until the aqueous layer is relatively
clear. Read the volume of H20 collected.
PHASE II. AQUEOUS PHASE
A. RESIDUE ON EVAPORATION, TOTAL SOLIDS, VOLATILE
SOLIDS, AND SUSPENDED SOLIDS
In appropriate evaporating (nonmetal1ic) dish, evaporate 100 mL of
solution on steam bath followed by drying, per current edition of "Standard
Methods for the Examination of Water and Wastewater."
202
-------
B. pH. TOTAL ACIDITY, AND ALKALINITY
Obtain pH of solution and measure acidity or alkalinity, per current
edition of "Standard Methods for the Examination of Water and Wastewater."
C. WATER SOLUBLE VOLATILE ORGANICS
Distill a 200-mL volume of sample at 95°C vapor temperature. Record
volume of organic liquid in distillate. Determine the density of the
organic liquid. Record result as percent by weight water soluble volatile
organics by multiplying the density by the volume.
D. GREASE
Place a sample of 500 mL - 1000 mL in a wide-mouth bottle. Extract
the grease with hexane per Standard Methods (Soxhlet Extraction). Correct
for residue left by hexane.
E. TOTAL LEAD IN AQUEOUS PHASE (API METHOD, pp. 747-763)
Pipette a 100 mL sample into a 400 mL beaker. Add 5 mL iodine solu-
tion and swirl to mix; add 20 mL of concentrated HNO^, cover with a
watchglass and heat to dryness. Dissolve the cooled residue in 20 mL of
dilute HN03 and filter through a Whatman No. 42 filter paper, if necessary,
into a 100 mL volumetric flask. Dilute to volume and aspirate into the
atomic absorption instrument against aqueous lead standards. Carry a
reagent blank with 100 mL of water.
PHASE III. SOLID PHASE
A. FLAMMABILITY
Place a small amount of dry solid phase on a spatula and place in
upper part of burner flame (in hood); note if material burns, color and
character of the flame, and if smoke or fumes are given off. Record
observations.
B. PERCENT INORGANIC AND ORGANIC (ASHING)
Weigh 5.00 grams of dry solid phase in a porcelain crucible. Heat (in
hood) to burn off majority of organics (if flammability test indicates a
high organic content). Place crucible in electric furnace and heat at
550°C for one hour; cool and weigh. Report percent organic and inorganic
content.
C. WATER EXTRACT
Weigh 20.00 grams of air-dry solid and add 100 mL of distilled water.
Heat to boiling while stirring solution. Filter and allow filtrate to
cool. On filtrate, determine pH and total residue on evaporation at 105°C.
Report water soluble residue in mg/g of solids.
203
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TABLE 1. METHODS FOR THE CHARACTERIZATION OF HAZARDOUS WASTES
Phase5
Liquid Organic Aqueous Solid
Flash pointb Total solids0 Flammabilityd
Distillate at 95°Cd Volatile solids0 Percent Organic0
Viscosityb pHd Percent Inorganic0
Organic groupsb Alkalinity or acidity0 Water Extract pH°
Water contentd Water soluble volatile Total Solids0
Others organicsd Others
Oil and grease0
Lead concentrationd
Others
Reparation of the three phases was made by centrifugation of the
sample for about 40 minutes at 1,000 RPM.
bAmerican Standards for the Testing and Materials.
°Standard Methods for the Examination of Water and Wastewater.
dSpecial Procedures of Sanitary Engineering Research Laboratories
(SERL), University of California, Berkeley.
REFERENCES
American Petroleum Institute, Division of Refining. 1969. Manual of Dis-
posal of Refinery Wastes, Volume 4. Washington, D.C.
American Public Health Association, American Water Works Association, and
the Water Pollution Control Federation. 1975. Standard Methods for
the Examination of Water and Wastewater, 14th edition.
American Society for Testing and Materials, Philadelphia, Pennsylvania.
Kolthoff, I. M. and E. B. Sandel 1. 1943. Textbook on Quantitative In-
organic Chemistry. MacMillan, New York.
Stephens, R. D. 1976. Hazardous Waste Sampling. In: Proceedings of
Hazardous Waste Research Symposium. Residual Management by Land
Disposal. EPA 600/9-76-015. U.S. Environmental Protection Agency.
Cincinnati, Ohio. NTIS No. PB 256-595.
204
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APPENDIX C
EAL CORPORATION REPORT DATED MARCH 13, 1981
ON THE CHEMICAL ANALYSIS OF FIVE WASTES
(GM/MS scans not included)
205
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EAL
CORPORATION
2030 Wright Avenue
Richmond, California 94804
(415) 235-2633
(TWX) 910-382-8132
March 13, 1981
Matrecon, Incorporated
Post Office Box 24075
Oakland, California 94623
Attention: Mr. Michael A. Fong
Reference: Purchase Order No. 1745
EAL Work Order No. 08300-000-0015
Dear Mr. Fong:
Enclosed please find our report for the five waste materials submitted
under the referenced purchase order for chemical analysis and GC/MS.
The analyses were performed in accordance with standard waste analysis
procedures as published by U.S. Environmental Protection Agency, and
ASTM. The methods are referenced on each of the individual test reports.
Our extraction procedure for the GC/MS study was modified somewhat from
EPA's scheme, and is fully discussed in the report.
We applied our Quality Control Program to all phases of the analyses in
order to assure the validity of the data. The program includes calibr-
ation curves, spikes, and blank determinations with each set of samples.
A full description of the QC program is found in Handbook for Analytical
Quality Control in Mater and Wastewater Laboratories, U.S. EPA-600/4-79-
019. QC data from this project, i.e., recovery, precision, and calibra-
tion information is available upon request.
Your billing for this report will be under separate cover. Your choice
of EAL for this study is greatly appreciated. Please call me with any
questions you may have concerning this report.
Sincerely,
BEC/pv Bent E. Christensen
Program Manager
206
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Matrecon, Inc.
Oakland, CA
1. Description
Form
Phases
Odor
March 13, 1981
Work Order 08300-000-0015
Purchase Order Ho. 1745
CHARACTERIZATION ANALYSES
FOR WASTE MATERIALS-GENERAL PHYSICAL TESTS
Lead Waste
1708-1-3
Dark brown liquid with sus-
pended and floating solids.
Spent Caustic
1701-1-5
Cloudy, yellow liquid with
white crystalline solids
at bottom
Separates by centrlfugatlon Aquous phase with solids.
into light brown aquous phase
with dark brown oil on top and
dark brown lumps floating on oil*
Strong gasoline odor*.
2. Specific Gravity Aquous Phase: 0.97 g/mL
Organic
(includes sus-
pended solids)
3. Organic/Inorganic/Water
Ratio (by weight)
Supporting Data
a) Total solids in
aquous phase, Z w/w
phase: 0.79 g/mL
13.6/0.19/86.2
0.35
b) Non-volatile solids at
550°C, in aquous phase, Z w/w 0.19
c) Water in organic phase
(Karl Fisher). Z, w/w
d) Total Organic Carbon (TOG)
Z, w/«
4. pH
5. Flash Point, °F
7.6
<32
Odorless
1.19 g/mL
3.4/23.5/73.1
26.9
23.5
1.07
7.7
Bolls without flashing
Pesticide Waste
1708-1-2
Cloudy, white liquid;
milky appearance
Aquous .
Weak phenol and chloro-
naphtalene odor.
1.00 B/mL
0.24/0.41/99.35
0.65
0.41
0.071
2.6
Boils without flashing
* Phase ratio (aquous/oil): By Volume: 84.2/5.8; By Height: 86.4/13,6
cpntinued
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Matrecon, Inc.
Oakland, CA
Page 2 - Characterization Analyses for Waste Materials-General Physical Tests
March 13, 1981
Work Order 08300-000-0015
Purchase Order No. 1745
Oil Pond 104 Waste
1701-1-4
Strong Acid Waste
1705-1-1
1. Description
Form
Phases
Odor
2. Specific Gravity:
(includes suspended solids)
3. ' Organic/Inorganic/Water
Ratio (by weight)
Supporting data
a) Total solids in aquous phase
%, w/w
b) Non-volatile solids at 550°C
in aquous phase, % w/w
c) Water in organic phase
(Karl Fisher), % w/w
d) Total Organic Carbon (TOG)
%, w/w
4. PH
5. Flash point, °F
Dark brown-black oil of tar-like
consistency.
Single organic phase.
Odor as used automobile oil.
Aquous phase:
Organic phase: 0.92 g/mL
99.0/0.39/0.61
0.61
Boils without flashing
Clear, yellow liquid.
Aquous
Weak with acid odor.
1.07 g/mL
2.62/1.12/96.26
3.74
1.12
0.78
0.5
Boils without flashing.
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Matrecon, Jnc,
Oakland, CA
HEAVY METALS BY ATOMIC ABSORPTION
ANALYSIS RESULTS
mg/ liter
narcn 11., LVOL
W,0, 08300-000-0015
P.O. No. 1745
Lead Waste
Aquous Organic
Phase Phase
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Barium
Cobalt
Molybdenum
Vanadium
Titanium
Organolead
Boron
1708-1-3
9.0
0.02
N.D.
N.D.
1.2
0.46
13
0.02
0.9
N.D.
N.D.
74
4.8
1.2
0.5
N.D.
3.0
200
9.6
500
0.02
N.D.
4.7
5.7
4.8
530
0.26
0.9
N.D.
0.2
N.D.
11
N.D.
43
0.1
3.5
38
Spent
Caustic
1708-1-5
50
N.D.
N.D.
0.6
N.D.
2.3
5.0
N.D.
1.8
N.D.
0.33
0.03
8.2
19
24
2.0
5.1
12
Pesticide
Waste
1708-1-2
9.0
N.D.
N.D.
N.D.
5.4
9.2
1.4
N.D.
24.5
N.D.
N.D.
N.D.
150
4.8
1.2
0.5
N.D.
3.0
--
26
Oil Pond 104
Waste
1708-1-4
500
N.D.
N.D.
8.0
286
33
170
4.0
N.D.
11.5
N.D.
450
N.D.
40
0.1
10.1
230
Strong Acid
Waste
1708-1-1
9.6
0.19
N.D.
0.22
22
5.6
28
N.D.
9.0
N.D.
N.D.
0.21
42
5.0
2.9
0.8
N.D.
19
Limits
of Detection
Aquous Organic
0.02 0.02
0.2 0.4
0.15
0.8
0.003
1.0 1,0
0.05
0,02 0.02
5
2.5
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Matrecon, Inc.
Oakland, California
CLASSIFICATION
OF ORGANIC CONSTITUENTS
March 13, 1981
P.O. 1745
W.O. 08300-0015
I. Functional Group Breakdown (ppm w/v):
Alkanes
Oxygenates
Olefins and Aromatic
Hydrocarbons
Lead Waste
1708-1-3
5000
100
25200
Method: ASTM D 1019-581;
II. Polarity Ranges (log
Lead Waste
1708-1-3
Fraction log p
ppm
2.6 3 . 93
11.8 4.62
15.6 5.43
9.8 6.27
2.6 7.22
0.26 7.94
0.52 8.69
p*), ppm w/v:
Pesticide Waste
1708-1-2
Fraction
ppm
1.3
0.66
1.2
0.88
0.38
0.29
0.28
Log p
3.93
4.46
5.07
5.87
6.80
7.81
8.87
Oil Pond 104 Waste
1708-1-4
11700
100
1500
GC-FID & Electrol.Cond.
Oil Pond 104
1708-1-4
Fraction
ppm
6900
16000
41000
31000
15000
4400
980
93
- OV101
Waste
Log p
3.53
3.93
4.68
5.43
6.27
7.20
7.94
8.32
Strong Acid Waste
1708-1-1
< 4
< 4
60
& FFAP.
Reference Table
Compound Log p
Acetone 0.55
Benzene 2 . 13
Naphthalene 3.37
Diphenyl Ether 4.20
4,4' - PCB 5.58
p,p' - DDT 6.19
Arochlor 1254 6.72
* log p = log 9n-octanol/water partition coefficient)
Method: Fed Reg. 43, No. 243, p. 58966, App. XI; HPLC - Micro Bondapak
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Matrecon, Inc
Oakland, California
HAZARDOUSNESS CHARACTERISTICS
REACTIVITY
March 13, 1981
P.O. 1745
W.O. 08300-0015
Lead Waste
1708-1-3
Spent Caustic
1708-1-5
Pesticide Waste
1708-1-2
Oil Fond Waste
1708-1-4
Strong Acid Waste
1708-1-1
I. Reaction With:
Water
Acid
Alkali
- No reaction
(raiscible)
- Forms dark
brown precipitate
Forms dark
brown precipitate
No reaction
(miscible)
Turns clear
and yellow
Forms white
precipitate
No reaction
(miscible)
Forms white
precipitate
Forms yellow to
brown precipitate
No reaction
(immiscible)
No reaction
(immiscible)
No reaction
(immiscibel)
No reaction
( miscible)
No reaction
(miscible)
Forms yellow
precipitate with
Method: Fed. Reg. 45, No. 98, p. 33122, § 261.23
II. Toxic Gas Evolution:
H2S - N.D.
HCN - 0.2 ppm
N.D.
0.8 ppm
N.D.
N.D.
N.D.
0.1 ppm
Method: Ibid and unpublished communication. EPA Washington, 1980.
N.D. = None Detected
generation of heat
N.D.
1.8 ppm
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EAL
CORPORATION
2030 Wright Avenue
Richmond. California 94804
(415) 235-2633
(TWX) 910-382-8132
ANALYSIS REPORT
Customer: Matrecon, Incorporated Date: March 11, 1981
Mr. Hike Fong .....
Pose Office Box 24075 Samples Received January 14 ,_ 1981
Oakland, California 94623 EAL W O No 08300-000-0015
Purchase Order No.: 1745
CC/MS Analysis of Hazardous Waste Samples
Sample
Three samples were submitted for GC/MS analyses:
Dismantling Pest. Waste EAL No. 1708-1-2
Lead Waste 1708-1-3
Oil Pond 104 1708-1-4
All three samples were adjusted to pH 11 with sodium hydroxide (NaOH) and ex-
tracted with methylene chloride (CH2C12) . The remaining solution was then acidified
to pH 2 with sulfuric acid (H2S04) and extracted with CH2C12. This is a standard
procedure for the separation of samples into base/neutral and acidic extractable
fractions prior to analysis for the organic priority pollutants. (EPA Method 625).
After extraction, the solvent was evaporated and the sample rediluted with one mL
of CH2C12
The ncid extractable fractions from all three samples and the base/neutral
fraction of the dismantling pest, waste (1708-1-2) were relatively clean and free
of oils and other materials that would prevent their analysis. Internal standard
was added to these fractions and they were analyzed without any further cleanup.
The base/neutral fractions of the lead waste (1708-1-3) and oil pond 104(1708-
1-4) contained large amounts of oil and other contaminants which EAL knows from
experience would make analysis impossible. These samples had to be processed further
before any analysis could be made. The oil and other material were removed from these
fractions by passing them through an alumina column and eluting the column with four
50 mL volumes of hexane, benzene, and chloroform.
Bent E. Christensen
Program Manager
EAL is an approved State of California chemical, radiological, bacteriological and fish toxicily bioassay
laboratory, an accredited American Industrial Hygiene Association laboratory: and a licensed clinical
laboratory.
212
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Page 2
Matrecon, Inc. March 11, 1981
Oakland, Ca. w_0_ 08300_000.0015
P.O. No. 1745
The hexane fraction contained oil and was not analyzed. The benzene and
firac chloroform fractions were free from oil and were evaporated and rediluted
to 1 mL with CH2C^and then analyzed after addition of internal standard. The
fourth fraction was not analyzed.
Analytical Methods:
The analyses were performed using a 30 meter SE-30 fused silica capillary
column (0.021 mm I.D.) connected directly to the source of the mass spectrometer.
The column was temperature programmed from 50*C to 3008C @ 8"C/min. 1.0 micro-
liters of each sample were injected onto the column using splitless injection.
The mass spectrometer was scanned from m/z 25 Co 450 in one second intervals. All
the data was stored on fixed discs. The amounts of the priority pollutants were
calculated from comparison to the internal standard using response factors created
from standard runs. The amounts of compounds similar in chemical structure to
the priority pollutants were calculated manually by using a response factor from
the similar priority pollutant and the area of the internal standard. All com-
pounds were identified using a computer library search.
Results and Discussion:
Because of the extremely complex nature of the samples, not all individual
components could be quanticated. Those that were are subject to error because
the solvent extraction and altmrfna column cleanup recoveries are uncertain and
the response factors used for compounds other than priority pollutants are approxi-
mate, in general, many of the compounds in the samples are chemically related to
the priority pollutants and in some cases, make up the bulk of the sample. Signi-
ficant differences in the chemical nature of the samples can be seen when the
percentages of the different classes of compounds in each sample are compared.
M-saant-lingr Pest. Waste (1708-1-2):
143 compounds were detected in this sample. Phenols accounted for 2IZ of
the acid fraction and their distribution is given in Table I. The other major
components of the sample were alcohols, ketones and some aldehydes.
5-ethyl-2-methylheptane accounted for 71% of the base neutral fraction. The
amounts of the base/neutral priority pollutants found are given in Table I.
213
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Page 3
Matrecon, Inc. March 11, 1981
Oakland, CA W.O. 08300-000-0015
P.O. No. 1745
Lead Waste (1708-1-3):
313 compounds were detected in this sample. The acid fraction contained
582 oxepane (a seven membered ring containing oxygen), 19Z diisooctylphthalate
and 72 phenols. The distribution of the phenols is given in Table II. The
remainder of the sample contained small percentages of aromatic and aliphatic
acids.
The base neutral fraction contained 122 substituted benzene; 32 naphthalenes;
102 phenanthrenes; 32 Fluorenes; 92 1,3-oxatniolane and 272 phthalates. The
priority pollutants found are listed in Table II.
Oil Pond (1708-1-4):
336 compounds were detected in this sample. The acid fraction contained
502 phenols, 142 benzoic acids and 132 aliphatic acids. The distribution of
the phenols is given in Table III.
The base/neutral fraction contained 342 phenanthrenes.. Phenanthrene it-
self accounted for approximately 3% of the sample. The priority pollutants
found in this sample are given in Table IV.
Summary:
Although the qualitative identification and quantitative estimates of
certain individual compounds may be subject to error, the data clearly indicates
that the samples contain significant amounts of organic compounds which are
chemically similar to the 129 priority pollutants listed in the Federal Register.
These include phenols, phthalates, naphthalenes, and phenanthrenes.
214
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Page 4
Matrecon, Inc. March 11, 1981
Oakland, CA W.O. 08300-000-0015
P.O. 1745
TABLE I
DISMANTLING PEST. WASTE
(1708-1-2)
Acid Fraction
Compound Concentration (ppm)
2-chlorophenol 3
2,6-dichlorophenol 4
2,3-dichlorophenol 2
2-chloro-6-methylphenol 1
4-(l,l-dimethylethyl) phenol 2
trichlorophenol 15
trichlorophenol 20
trichlorophenol 78
2,5-dichlorophenol 78
2,3-dichlorophenol 57
Base Neutral Fraction
Compound Concentration (ppm)
n-nitrosodiphenylamine 3
di-n-butylphthalate 8
butyl-benzylphthalate 3
215
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Page 5
Matrecon, Inc.
Oakland, CA
March 11, 1981
Work Order 08300-000-0015
P.O. Mo. 1745
TABLE II
LEAD WASTE
(1708-1-3)
Compound
2-aethylphenol
2, 6-dimethylphenol
2-«thylphsnol
3 , 4-dimethylphenol
2 , 3-dloethylphenol
2,3, 5-er±m*tnylph«nol
2-ethyl-5-ffl«thylphenol
4-ethyl-2-Mthylph«nol
2-ethyl-4-««thylph«nol
2 , 3 , 5- er&MChylphuol
2,4,5- cr±»«thylph«nol
2, 4-diawthylphanol
Comoound
Acid Fraction
Z of Total
0.72
0..5
0.26
0.68
0.94
0.18
0.21
0.25
0.70
0.95
1.17
1.5
Base/Neutral Fractic
(ppm)
Sample Anoroxlaate Concentration
33
23
12
32
44
3
10
11
32
45
55
74
£ (PP»)
Approximate Concentration*
Anthracene
di-m-butylphthalate
fluoranthene
bucylbenzylphchalace
chrysene
benzo(a)pyrene
14
1
9
1.5
4
3.4
weak spectra obtained - tentative identification and quantitation.
216
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Page 6
Matrecon, Inc.
Oakland, CA
March 11, 1981
W.O. 08300-000-0015
P.O. No. 1745
TABLE III
OIL POND 104
(1708-1-4)
Acid Fraction
Compound
phenol
2-methylphenol
4-raethylphenol
2,6-dimethylphenol
2-ethylphenol
2,3-dimethylphenol
2,4-dimethylphenol
2,5-dimethylphenol
3,4-dimethylphenol
2-(1-methylethyl)phenol
4-ethyl-2~raethylphenol
4-ethyl-3-methylphenol
2-ethyl-4-methylphenol
2,3,5-trimethylphenol
2,4,5-trimethylphenol
4-ethyl-5-methylphenol
3-(1,l-dimethylethyl)-phenol
5-methyl-2-(1-methylethyl)phenol
Approximate Concentration (ppm)
85
67
328
7
35
248
364
90
127
16
41
42
142
46
64
29
63
17
217
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Page 7
Matrecon, Inc. March 11, 1981
Oakland, CA w_0> 08300_000-0015
P.O. No. 1745
TABLE IV
OIL POND 104
(1708-1-4)
Base/Neutral Fraction
Compound Approximate Concentration (ppm)
naphthalene 4
fluorene 4
phenanthrene 185
anthracene 19
di-n-butylphthalate 13
pyrene 6
butylbenzylphthalate 13
chrysene 117
benzo(a)anthracene 106
n-nitrosodiphenylamine 17
218
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APPENDIX n
MAJOR EXTRACTABLE ORGANICS RECOVERED FROM WASTES DETERMINED BY GAS CHROMATOGRAPHY
AND MASS SPECTROSCOPY (GC/MS)
Lead waste
Compound
2,2,4-trimethyl
oxepane
Oii society ]phtha late
2, 4-dlmethyl phenol
1,3-oxathiolane
Benzeneacetic acid
Phenanthrene
caboxylic acid
2,4,5-trimethyl
phenol
2,3,5-trimethyl
phenol
2, 3-di methyl phenol
2-methyl phenol
3,4-rtimethylphenol
2-ethyl -4-methyl
phenol
2, 6 -dimethyl phenol
3-methylphenanthrene
Anthracene
2-ethylphenol
4-ethyl-2-methyl
phenol
2-ethyl-5-methyl
phenol
Fluoranthene
Chrysene
Benzo (a) pyrene
Rutyl benzyl phthal ate
Olbutylphthalate
ppm
2500
800
74
62
59
55
55
45
44
33
32
32
23
21
14
12
11
10
9
4
3.4
1.5
1
Pesticide waste
Compound ppm
5-ethyl -2-methyl 1700
heptane
Trichlorophenol(s) 113
l-(2-chlorophenyl) 87
ethanol
2,5-dichlorophenol 78
2,7-dimethyl 76
naphthalene
Pentafluorophenol 74
1,3-oxathiolane 66
2,3-dichlorophenol 59
2-butoxyethanol 51
l-(2-butoxyethoxy) 50
ethanol
Dibutyphthalate R
2,6-dichlorophenol 4
2-chlorophenol 3
N-nitroso 3
(liphenylami ne
Butyl benzyl phthal ate 3
4-(l,l-dimethyl ethyl) 2
phenol
2-chloro-6-methyl 1
phenol
Oil Pond 104
Compound
Dichloromethane
2,4-riipiethylphpnol
4-(l,l-dimethyl ethyl)
henzoic acid
4-methyl phenol
2,3-dimethylphenol
Di isooctylphthalate
Phenanthrene(s)
2-ethyl -4-methyl
phenol
3-methylcinnoline
3, 4 -dimethyl phenol
Chrysene
Benzo(a)anthracene
2, 5-di methyl phenol
Phenol
2-methyl phenol
2.4,5-trimethyl
phennl
3-(l,l-dimethylethyl)
phenol
2.3,5-trimethyl
phenol
4-ethyl-3-methyl
phenol
2-ethyphenol
4-ethyl-5-methyl
phenol
Anthracene
N-nitroso
diphenyl ami ne
2-nethyl-2-(l-methyl-
ethyl ) phenol
Dihutyiphthalate
Butyl benzyl phthal ate
2, 6 -dimethyl phenol
Pyrene
Naphthalene
Fluorene
ppm
450
3fiO
340
330
250
190
190
140
140
127
117
106
90
85
67
64
63
«6
42
35
29
19
17
7
13
13
7
6
A
4
219
-------
APPENDIX E
MATERIALS FOR SOIL AND ADMIX LINERS
Material
Supplier
Soil
Fine-grain, high silica content
Mare Island Naval Shipyard,
Vallejo, California
Soil cement
Soil: "Waste fines" from rock
crushing
Cement: Type 1-2-5 Portland cement
Rice Hull ash (RHA) cement
Coating C: Coal-tar epoxy, Ceilcote
Flake Prime and Flake Tar
Coating K: Coal-tar epoxy,
Bitumastic 300M
Hydraulic asphalt concrete (HAC)
Hot mix
Aggregate, dense-graded 0.25-in. max.
Asphalt, AR-4000
Modified bentonite
Sand, dense-graded No. 2 (contained
1% water)
Quarry Products Company,
Richmond, California
Kaiser Permanente
Industrial Materials Co.,
Los Angeles, California
Ceilcote
Koppers
Ransome Co.,
Emeryville, California
Lone Star Quarry,
Livermore, California
Douglas Oil Company
Topsoil King,
Richmond, California
220
-------
APPENDIX F
PROPERTIES OF UNEXPOSED POLYMERIC MEMBRANES3
Polymerb
Compound type''
Fabric, type
Thread count , epi
Nominal thickness, rail
Matrecon liner serial number6
Analytical properties:
Specific gravity
Ash (db)f, J
Volatiles, %
Extractables (db)f, 1
Solvent9
Physical properties:
Average thickness, mil
Tensile at fabric break, ppi
Elongation at fabric break, %
Tensile at ultimate break, psi
Tensile at ultimate break, ppi
Elongation at break, I
Tensile set, %
S-100, psi
S-100, ppi
S-200, psi
S-200, ppi
Tear strength (Die C), Ib
Tear strength (Die C), ppi
Puncture resistance:
Thickness, mil
Stress, Ib
Elongation, in.
Hardness, Durometer points
Direction
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Butyl
XL
62 '.5
44
1.176
4.28
0.46
11.79
MEK
62
...
...
...
1625
1570
104.1
100.2
415
470
18
18
335
280
21.4
17.9
750
615
48.0
39.2
12.88
14.05
201
221
62
39.5
1.17
54A
Butyl
XL
Nylon
22x11
34
57R
1.286
23.46
0.29
6.36
MEK
34
73.1
72.3
25
25
h
h
h
h
60
25
4
2
...
...
...
...
...
...
...
34
26.6
0.26
71A
CPE
TP
30
77
1.362
12.55
0.14
9.13
n-heptane
29
...
2055
2340
59.6
66.7
325
480
140
160
1240
560
36.0
16.0
1540
820
44.7
23.4
7.83
6.93
273
239
29
43.9
0.94
BOA
CPE
TP
22
86
1.377
17.37
0.05
6.02
n-heptane
22
...
...
1845
1510
40.6
34.1
355
595
208
235
870
275
19.1
6.2
1210
405
26.6
9.2
4.05
3.91
187
178
22
20.9
0.91
67A
CPE
XL
36
100
1.390
6.02
0.66
17.42
n-heptane
36
...
...
1880
1935
67.6
69.6
460
400
43
33
555
680
20.0
24.4
1295
1455
46.5
52.3
10.58
10.68
297
304
35
40.0
0.95
63A
CSPE
TP
Nylon
8x8
31
6R
1.343
3.28
0.51
3.77
DMK
31
37.7
34.0
30
15
1845
1610
59.7
52.5
245
240
97
93
995
880
32.2
28.7
1710
1390
55.4
45.3
...
...
34
33.7
0.59
77A
Continued
221
-------
APPENDIX F (Continued)
Polymer'1
Compound type^
Fabric, type
Thread count, epi
Nominal thickness, mil
Matrecon liner serial number6
Analytical properties:
Specific gravity
Ash (db)f, %
Volatlles, %
Extractables (db)f, %
Solvent9
Physical properties:
Average thickness, mil
Tensile at fabric break, ppi
Elongation at fabric break, %
Tensile at ultimate break, psi
Tensile at ultimate break, ppi
Elongation at break, %
Tensile set, %
S-100, psi
S-100, ppi
S-200, psi
S-200, ppi
Tear strength (Die C) , Ib
Tear strength (Die C) , ppi
Puncture resistance:
Thickness, mil
Stress, Ib
Elongation, in.
Hardness, Durometer points
Hardness, Durometer points
Direction
of test
Machi ne
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machi ne
Transverse
Machine
Transverse
Machi ne
Transverse
Machine
Transverse
Machine
Transverse
CSPE
TP
35
55
1.371
3.32
0.42
4.08
DMk
35
...
...
1860
1565
65.0
55.1
260
300
75
97
1110
650
38.9
23.1
1810
1205
63.3
42.5
10.31
9.57
294
271
35
45.0
0.83
78A
32D
CSPE
TP
'33
85
1.311
4.02
0.92
8.22
DMK
33
...
2345
2055
75.0
66.2
260
325
167
192
1150
750
36.8
24.2
2130
1410
68.2
66.2
9.77
8.78
308
277
33
47.8
0.86
79A
...
CSPE
TP
Polyester
8x8
30
125R
1.296
3.99
0.12
8.97
DMK
29
53.4
41.4
19
33
53.0
46.6
220
245
73
83
41.8
29.0
...
51.8
42.5
...
...
28
30.6
0.61
75A
28D
ELPO
CX
-22
36
0.938
0.90
0.15
5.50
MEK
23
...
...
2715
2525
61.0
55.6
675
655
465
445
940
905
21.1
19.9
1035
1000
23.2
22.0
8.90
8.23
388
369
22.5
26.3
0.97
89A
32D
EPDM
XL
62!s
8
1.173
6.78
0.38
23.41
MEK
62
...
1635
1550
98.9
94.9
520
500
14
11
350
320
21.2
19.6
800
740
48.4
45.3
12.7
12.8
206
211
60
56.9
1.46
67A
...
EPDM
XL
'30
26
1.169
7.67
0.50
22.96
MEK
36
...
...
...
1935
1865
74.5
70.9
440
460
9
9
385
330
14.8
12.5
925
830
35.6
31.5
7.33
7.47
193
197
37
31.3
1.24
58A
...
EPDM
TP
Polyester
8x8
40
83R
1.199
0.32
0.31
18.16
MEK
39
43.2
29.0
20
1010
870
39.7
34.8
265
240
59
51
890
730
35.0
29.2
990
845
38.9
33.8
39
33.6
0.61
70A
Continued
222
-------
APPENDIX F (Continued)
Polymerb
Compound type''
Fabric, type
Thread count, epi
Nominal thickness, mil
Matrecon liner serial number6
Analytical properties:
Specific gravity
Ash (db)f, %
Volatiles, %
Extractables (db)f, %
Solvent9
Physical properties:
Average thickness, mil
Tensile at yield, ps1
Tensile at yield, ppi
Tensile at break, psi
Tensile at break, ppi
Elongation at break, %
Tensile set, %
S-100. psi
S-100, ppi
S-200, psi
S-200, ppi
Modulus of elasticity, psi
Tear strength (Die C), Ib
Tear strength (Die C), ppi
Puncture resistance:
Thickness, mil
Stress, Ib
Elongation, in.
Hardness, Durometer points
Hardness, Durometer points
Direction
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
EPDM
XL
'H
91
1.160
7.33
0.34
23.64
MEK
37
...
...
...
1865
1790
67.2
66.3
475
500
11
10
375
300
13.5
11.2
915
795
32.9
29.5
...
7.27
7.16
196
195
37
29.2
1.17
52A
...
HOPE
CX
100
99
0.943
0.10
0.06
...
103
2715
2640
306.5
291.9
2185
2195
246.5
231.4
750
675
640
585
1965
1920
221.7
212.3
1980
1945
223.5
215.2
78,600
78,700
...
...
...
...
99
131.0
0.33
95A
59D
HDPEC
CX
'si
105
0.948
0.03
0.14
0.00
MEK
32
3745
3815
118.4
122.9
2610
2355
81.3
75.8
100
125
85
107
2635
2385
82.2
74.7
...
...
...
150,150
158,750
40.17
36.00
1215
1110
32
51.2
0.25
90A
60D
LDPEC
CX
io
21
0.931
0.00
0.09
3.60
MEK
9
1490
1175
14.2
10.7
2990
2940
28.4
26.8
510
675
395
535
1490
1175
14.2
10.7
1610
1165
15.3
10.6
19,400
24,400
4.07
3.54
420
365
9.6
13.7
0.79
86A
41D
LDPEC
CX
'si
108
0.921
0.04
0.18
2.07
MEK
31
1455
1455
41.6
41.8
2085
1975
59.7
66.6
535
575
435
470
1375
1265
39.4
36.2
1385
1300
39.5
37.2
21,960
24,870
14.96
13.91
516
479
31
33.5
0.51
93A
38D
Neoprene
XL
'H
43
1.477
12.30
0.45
13.69
DMK
33
* * *
...
* *
...
1910
1660
65.9
56.0
330
310
8
6
490
430
16.9
14.5
1105
970
38.1
32.7
...
...
5.40
5.43
171
170
33
30.6
1.14
57A
Neoprene
XL
62!5
82
1.480
13.21
0.19
13.43
DMK
61
...
*
...
1835
1675
113.8
100.2
390
410
10
9
405
360
25.1
21.5
875
705
54.3
42.2
...
11.57
10.70
183
178
60
53.9
1.29
57A
...
Continued
223
-------
APPENDIX F (Continued)
Polymer^
Compound typed
Fabric, type
Thread count, epi
Nominal thickness, mils
Matrecon liner serial number6
Analytical properties:
Specific gravity
Ash (db)f, %
Volatile*. %
Extractables (db)f, %
Solvent9
Physical properties:
Average thickness, mil
Tensile at yield, psi
Tensile at yield, pp1
Tensile at break, psi
Tensile at break, ppi
Elongation at break, %
Tensile set, %
S-100, psi
S-100, ppi
S-200, psi
S-200, ppi
Modulus of elasticity, psi
Tear strength (Die C) , Ib
Tear stength (Die C), ppi
Puncture resistance:
Thickness, mil
Stress, Ib
Elongation, in.
Hardness, Durometer points
Hardness, Durometer points
Direction
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Neoprene
XL
'37
90
1.390
4.67
0.37
21.46
DMK
37
...
...
2185
2010
80.9
74.4
415
415
26
25
565
650
21.0
20.4
1450
1225
53.7
45.3
...
7.74
7.29
207
196
37
44.9
1.01
61A
...
Polybutylene0
CX
8
98
0.915
0.08
0.12
> .
...
8
i *
...
5625
5580
42.8
44.6
390
375
346
331
2330
2360
17.7
18.9
3035
3200
23.1
25.6
...
...
2.61
2.85
355
380
7.5
13.9
0.66
94A
. . .
Polyester
CX
"?
75
1.236
0.38
0.26
2.74
MEK
7
...
...
...
6770
6765
47.4
47.4
560
590
340
370
2715
2455
19.0
17.2
2880
2585
20.2
18.1
...
...
6.38
5.47
911
782
7.8
29.9
1.30
93A
49D
Polypropylene*-
CX
33
106
. . .
0.01
. . <
...
33
5015
5020
162.5
160.9
1
3036
i
99.5
40
75
16
50
...
3055
...
100
*
...
...
190,900
184,300
12.25
9.37
393
302
33
60.3
0.65
...
68D
PVC
TP
'30
11
1.276
6.14
0.15
33.90
CC14
30
...
. . .
3005
2750
90.2
82.5
350
365
91
106
1495
1345
44.9
40.4
2140
1885
64.2
56.6
11.37
11.04
379
368
31
38.6
0.64
80A
...
PVC
TP
20
17
1.254
5.81
0.44
34.11
+ CH30H
20
2910
2675
56.7
52.2
350
365
70
83
1360
1180
26.5
23.0
1915
1690
37.3
33.0
6.56
5.94
332
301
20
25.30
0.70
76A
29D
Continued
224
-------
APPENDIX F (Continued)
Polymerb
Compound typed
Fabric, type
Thread count, epi
Nominal thickness, mil
Matrecon liner serial number6
Analytical properties:
Specific gravity
Ash (db)f, %
Volatiles, %
Extractables (db)f, %
Solvents
Physical properties:
Average thickness, mil
Tensile at break, psi
Tensile at break, ppi
Elongation at break, %
Tensile set, %
S-100, psi
S-100, ppi
S-20U, psi
S-200, ppi
Tear strength (Die C), Ib
Tear strength (Die C), ppi
Puncture resistance:
Thickness, mil
Stress, Ib
Elongation, in.
Hardness, Durometer points
Di rection
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
PVC
TP
20
19
1.231
3.65
0.05
38.91
22
2495
2335
52.2
19.0
310
340
55
71
1410
1250
29.5
26.3
1935
1675
40.5
35.1
6.49
6.05
295
275
22
24.0
0.71
72A
...
PVC
TP
30
59
1.280
6.97
0.31
35.86
33
2685
2430
87.5
79.2
355
395
45
56
1020
970
33.3
31.6
1715
1445
55.9
47.1
10.25
9.54
313
290
32
40.0
0.75
73A
26D
PVC
TP
20
88
1.255
2.80
0.17
33.46
CC14
20
3395
2910
67.9
58.2
325
335
102
101
1870
1600
37.4
36.0
2610
2190
52.2
43.8
9.26
9.17
463
470
20
28.6
0.56
80A
...
PVC
TP
10
89
1.308
5.67
0.03
25.17
+ CH^OH
a
3715
3085
40.9
33.9
315
325
195
205
1845
1530
20.3
16.8
2715
2195
29.9
24.1
4.49
4.30
408
391
11
17.0
0.48
82A
...
PVC
TP
20
92
...
5.84
0.06
32.75
20
2435
2145
48.7
42.9
245
255
43
48
1515
1365
30.3
27.3
2170
1885
43.4
37.7
8.70
7.46
435
373
20
27.4
0.62
8?A
SOD
PVC
TP
10
93
1.283
4.94
0.12
32.26
11
3575
3035
38. 1
33.4
325
350
98
117
1750
1420
18.7
15.6
2580
2055
27.5
22.6
4.26
3.99
400
362
11
15.9
0.55
78A
...
aMethods used for determining properties of unexposed polymeric membranes; ASTM 0297, Method A for specific
gravity; ASTM 0297 for ash; volatiles was defined as percent weight loss after 2 hours at 105°C; Matrecon
Test Method No. 2 for extractables (Matrecon, 1983, pp 340-43); ASTM D412 for tensile properties using the
Type IV test specimen; ASTM D638 for tear strength; ASTM 0882 modified, for modulus of elasticity; FTMS 101B,
Method 2065 for puncture resistance; and ASTM 02240 for hardness. Note that all tensile and tear testing re-
ported in this appendix was done at 20 ipm.
bCPE = Chlorinated polyethylene; CSPE = chlorosulfonated polyethylene; ELPO = elasticized polyolefin; EPDM =
ethylene propylene rubber; PVC = polyvinyl chloride.
cUnpigmented, i.e. compounded without a filler.
dXL = Crosslinked; TP = Thermoplastic; CX = Crystalline.
Contractors' identification number. R = Fabric-reinforced.
fdb = Dried basis.
9MEK = Methyl ethyl ketone; DMK - dimethyl ketone = acetone; CC14 + CH3UH = 2:1 blend of carbon tetrachloride
and methyl alcohol.
"Bulk of lining materials' strength is in the nylon fabric. The butyl coating over the fabric tended not to
fail catastrophically, and no useful value could he obtained for tensile strength at ultimate break.
'Sheeting tended to fail after yielding and no value could be determined for a catastrophic failure.
225
-------
APPENDIX G
PHYSICAL PROPERTIES OF UNEXPOSED CRYSTALLINE POLYMERIC MEMBRANES3
TESTED AT TWO INCHES PER MINUTE
Polymer13
Nominal thickness, mil
Matrecon liner serial number
Physical properties
Tensile at yield, psi
Tensi le at yield, ppi
Elongation at yield, %
Tensi le at break, psi
Tensile at break, ppi
Elongation at break, %
Tensile set, %
S-100, psi
S-100, ppi
S-200, psi
S-200, ppi
Tear strength (Die C), "Ib
Tear strength (Die C), ppi
aTensile properties measured
accordance with ASTM D638.
Di rection
of test
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
Machine
Transverse
on 0.25 in. wide
Tear resistance
HOPE
100
99
2385
2460
265
244
15
15
3915
4440
437
441
925
1015
819
900
1660
1720
184
170
1655
1720
184
170
87.2
88.9
839
850
"special
measured
HDPEC
32
105
3695
4020
111
121
17
22
4270
3295
129
98.8
825
860
715
715
2725
2440
82.1
73.2
2725
2460
82.1
73.9
32.4
28.1
992
897
LDPEC
10
21
1205
1015
11.1
9.7
28
18
2845
2645
26.1
25.2
490
635
365
515
1445
1105
13.2
10.5
1610
1125
14.8
10.7
3.9
3.7
424
400
" dumbbel 1 tested at 2
in accordance with ASTM
LDPEC
30
108
1270
1255
37.7
36.9
20
18
1690
1645
50.2
48.2
515
535
400
430
1230
1190
36.6
34.9
1185
1145
35.2
33.6
14.2
12.6
462
421
inches
D1004
Polypropyl enec
33
106
4960
4785
162
159
7
6
580U
4570
190
152
665
640
560
545
3255
2820
106
93.9
3400
3080
111
103
35.3
31.7
1082
987
per minute in
at a test speed
of 2 in. per minute.
bHDPE = High-density polyethylene; LDPE = low-density polyethylene.
Compounded without pigment.
226
-------
APPENDIX H
MATERIALS USED IN CONSTRUCTING PRIMARY EXPOSURE CELLS
AND MOUNTING LINER SPECIMENS
Material
Epoxy resins
Epoxy 1
Use
To cast epoxy rings
for sealing liners
in cells9
Trade name
Concresive 1217
Supplier
Adhesive En-
gineering
Epoxy 2
Epoxy 3
Epoxy 4
To coat inner walIs
of cells and bases;
to cast sealing rings3
To cast epoxy rings3
To seal 2-in. cylin-
drical specimens in
glass cylinders
Concresive 1305
Concresive 1310
Concresive 1001
Adhesive En-
gineering
Adhesive En-
gi neering
Adhesive En-
gi neering
Paints
Primer
Caulks
Butyl rubber
Polysulfide
Gasket
Neoprene sponge
To coat inner sur-
face of cells before
coating with epoxy
To seal membrane
specimens in cells
To seal membrane
specimens in cells
To seal liners in pri-
mary exposure cells
Koropon CA
Sure-Seal
De Soto,
Berkeley, CA
Carlisle,
Carlisle, PA
Col ma Joint Sealer Sika,.Lynd-
(Sikaflex 412) hurst, NJ
Cal Neva,
Oakland, CA
Silica gravel
Inert gravel for
base of eel Is.
G.E. Dodson
Auburn, CA
Sandblasting sand
To cast epoxy rings
to use on inside
surfaces of spacers
Clementina No. 2
Clementina,
Berkeley, CA
aThe first rings were made with Epoxy 1; however, as Epoxy 2 and 3 are more
resistant to chemicals and solvents, we decided to use them in the remain-
der of the cells.
227
-------
APPENDIX I
PHYSICAL PROPERTIES OF PRIMARY LINERS AFTER WASTE EXPOSURE IN CELLS
Analytical
properties
Exposure
ro
ro
Co
Liner
Polymer no. Waste3
Butyl 57R
HN03-HF-HOAc (W-9)
Pesticide (W-ll)
Pb waste (W-14)
Spent caustic (W-2)
Time,
days
Unexp.
505
1218
500
1258
499
1339
526
1249
Thick-
ness,
mil
34
34
37
35
34
35
34
34
34
Vola-
tiles,
%
0.29
5.92
11.46
4.10
4.79
2.79
3.53
1.75
1.37
Extract-
ables,
%
6.36
*
8.65
5.15
7.62
7.75
7.86
7.86
Physical properties
Puncture
resistance
Tensile
strength11
72.7 ppic
96
94
111
93
97
98
104
100
Elonga-
tionb
42%d
60
645
143
100
119
167
60
219
Tear
S-100h S-200b strength11
... ... ...
Retention of properties, %
...
...
...
... ... ...
Stress
26.6 Ib
85
85
97
105
91
94
104
113
Elong-
ation
0.26 in.
92
100
123
131
108
119
92
131
Hardness
Duro Duro
A D
71A
Change in
points
-4A
-5A
-4A
+ 1A
-4A
-8A
-2A
-2A
Continued
-------
APPENDIX I. (Continued)
ro
ro
Analytical
Physical properties
properties
Polymer
Chlori-
nated
poly-
ethy-
lene
Exposure
Liner Time,
no. Wastes days
77 Unexp.
HN03-HF-HOAc (W-9) 459
1218
Oil Pond 104 (W-5) 521
1358
Pesticide (W-ll) 500
1258
Pb waste (W-14) 499
1344
Spent caustic (W-2) 526
1249
86 Unexp.
50% Well 118/ 985
50% H20
Thick-
ness,
mi 1
29
32
35
36
38
31
32
36
40
28
29
?2
26
Vola-
tiles,
%
0.14
7.82
13.18
3.69
10.11
4.99
7.91
11.58
19.20
2.32
2.79
0.05
16.50
Extract-
ables,
%
9.13
10.09
9.41
17.00
9.72
9.41
7.31
7.24
...
9.10
10.77
Puncture
resistance
Tensile
strength*1
2197 psi
93
101
55
58
96
101
68
66
93
114
1677 psi
83
Elonga-
tion*1
402%
89
89
98
88
100
89
101
83
107
88
475%
81
S-lOQh
900 psi
Retention
97
113
53
62
94
113
56
71
87
129
572 psi
Retention
84
S-200*1
1180 psi
Tear
strength"
7.38 In
Stress
43.9 Ih
Elong-
ation
0.94 in.
of properties, %
102
118
58
68
98
118
60
76
84
131
807 psi
82
75
55
63
99
104
77
83
84
100
3.98 ppi
95
108
70
88
109
108
79
77
102
95
20.9 In
99
101
101
133
112
101
98
99
120
85
0.91 in.
of properties, %
90
107
132
104
Hardness
Ouro Duro
A D
80A
Change in
points
-8A
-13A
-30A
-16A
-3A
-6A
-13A
-21A
-5A
-3A
67A
Change in
points
-5A
Cont i nupd
-------
APPENDIX I. (Continued)
CO
o
Polymer
Chi orosul -
fonated
polyethy-
lene
Exposure
Liner 1 1 me ,
no. Waste3 days
6R Unexp.
HN03-HF-HOAc (W-9) 505
1218
Oil Pond 104 (W-5) 521
1357
Pesticide (W-ll) 504
1258
Pb waste (W-14) 499
1343
Spent caustic (W-2) 526
1249
125R6 Unexp.
D.I. Water (W-18) 985
Well 118 (W-17) 990
Analytical
propert i es
Thick-
ness,
mi 1
31
35
35
41
42
35
33
36
37
33
34
33
37
38
Vola-
tiles,
%
0.51
4.69
7.18
7.51
10.25
8.00
9.73
10.78
11.44
4.77
5.77
0.12
14.45
9.03
Extract-
ables,
%
3.77
4.'62
9i45
4.13
5.39
3.52
5.95
3^79
8.97
7.77
8.70
Physical properties
Tensi le
strength11
1727 psi
116
134
130
108
120
137
116
134
153
167
49.8 ppi
107
116
Puncture
resistance
El onga -
tionh
242%
90
79
103
72
112
85
107
77
70
65
233%
113
101
S-100h
937 psi
Retent i on
10>
112
63
96
90
118
85
118
165
POO
35.4 ppi
Retenti on
89
96
Tear
S-200b strength11
1550 psi
of properties , %
106
74
96
109
149
104
78
...
47.2 ppi
of properties , %
101
114
Stress
33.7 Ib
135
136
162
177
125
162
153
151
154
ISO
30.6 Ib
128
138
El ong-
at ion
0.59 in.
112
115
147
139
132
141
120
119
90
114
0.61 in.
75
128
Hardness
Huro Duro
A D
77A
Change in
points
-3A
-4A
-32A
-17A
-4A
-4A
-11A
-13A
-2A
+2A
75A 2811
Change in
points
-11A -20
-5A -13D
Cont i nued
-------
APPENDIX I. (Continued)
ro
GO
Exposure
Liner Time,
Polymer no. Waste3 days
Elasti- 36 Unexp.
cized
polyole-
fln
Analytical
properties
Thick-
ness,
mi 1
23
Vola-
tiles,
%
0.15
Extract-
ables,
%
5.50
Physical properties
Tensile
strength*3
2620 psi
Elonga-
tionh
665
S-lOQb
922 psi
S-200b
1017 psi
Tear
strength*1
8.56 Ib
Puncture
resistance
Stress
26.3 Ih
Elong-
ation
0.97 in.
Retention of properties, %
Slurry oil (W-15) 327
2355
HN03-HF-HOAc (W-9) 505
1217
Oil Pond 104 (W-5) 521
1357
Pesticide (W-ll) 494
2699
Pb waste (W-14) 499
1343
Spent caustic (W-2) 526
2677
Well 118 (W-17) 990
50% Well 118/
50% H20 (W-21) 985
Ceionized H20 (W-18) 981
HFL (W-10) 2293
Slop water (W-4) 2299
26
26
24
23
26
27
24
23
24
23
23
24
24
24
21
23
25
0.38
4.02
3.20
5.26
2.15
5.12
0.13
0.58
1.03
1.53
1.25
1.01
1.17
1.23
0.57
1.46
...
23.88
5.40
7.09
20.74
7.14
6.86
5.66
8.06
5.96
4.90
5.48
A-
5.19
5.40
...
67
57
98
98
44
52
102
96
72
86
90
94
94
98
101
100
80
96
97
99
96
86
78
101
97
92
94
100
97
96
98
96
98
88
70
60
92
98
61
71
104
91
95
104
87
87
103
103
104
98
97
68
58
96
99
59
69
107
91
92
102
88
88
100
100
102
98
95
76
127
109
100
56
76
103
89
96
113
103
92
110
107
93
98
91
114
70
152
135
85
86
130
103
113
118
111
98
127
111
106
110
145
164
107
146
128
120
124
130
113
119
119
111
110
137
104
94
118
140
Hardness
Duro Ouro
A n
89A 32D
Change in
points
-12A
-27A -110
-5A
-3A
-ISA
-16A
-1A
OD
-2A
-9A -ID
-4A
+ 1D
-3A + 2D
-1A OD
-8A OD
00
-16A -2D
Continued
-------
APPENDIX I. (Continued)
Analytical
Physical properties
properties
ro
CO
ro
Exposure
Liner Time,
Polymer no. Waste3 days
Ethylene 26 Unexp.
propylene
rubber
HN03-HF-HOAc (W-9) 497
1147
Pesticide (W-ll) 500
1258
Pb waste (W-14) 499
1344
Spent caustic (W-2) 526
1249
Thick-
ness,
mi 1
36
37
38
39
38
38
39
33
38
Vola-
tiles,
%
0.50
8.95
12.02
3.34
6.29
2.83
5.25
1.27
1.31
Extract-
anles,
%
22.96
21.36
27.76
23.13
25.20
22.27
26.01
23.95
Puncture
resistance
Tensile
strength*5
1900 psi
91
79
96
96
92
94
104
102
El onga-
tionh
450%
97
94
100
104
100
106
102
95
S-100h
357 psi
Retention
81
70
89
87
84
80
88
108
Tear
S-200h strength0
877 psi 7.40 Ih
of properties, %
93 88
81 87
96 103
67 98
92 86
92 101
86 90
112 103
Stress
31.3 Ib
118
105
110
104
94
104
103
118
El ong-
ation
1.24 in.
106
100
110
108
93
113
99
111
Hardness
Duro Duro
A D
58A
Change in
points
-8A
-12A
-5A
-6A
-1A
-8A
-2A
-2A
Continued
-------
APPENDIX I. (Continued)
ro
OJ
CO
Analytical
properties
Exposure Thick- Vola- Extract-
Liner Tine, ness, tiles, ahles, Tensile
Polymer no. Waste3 days mil % % strengthb
Neoprene 43 Unexp. 34 0.45 13.69 1758 psi
Basin F (W-16) 136 38 11.92 ... 84
1386 37 9.11 13.50 60
Oil Pond 104 (W-5) 521 41 12.99 ... 59
1356 38 21.31 15.86 62
Pesticide (W-ll) 494 37 11.29 13.25 80
1257 38 13.63 16.14 61
Pb waste (W-14) 499 42 18.01 8.95 52
1342 43 17.50 12.15 56
Spent caustic (W-2) 526 33 4.40 ... 98
1237 35 5.67 13.69 100
Well 118 (W-17) 136 41 15.53 ... 70
1368 42 25.88 12.11 52
Physical properties
Flonga-
tionb
320%
88
70
86
92
93
83
76
75
98
95
82
69
S-100h
460 psi
Retention
83
105
50
42
62
54
53
61
90
95
65
66
S-200b
1037 psi
Tear
strength*1
5.41 Ih
Puncture
resistance
Stress
30.6 Ib
Elong-
ation
1.14 in.
of properties, %
94
95
67
51
79
70
71
75
98
105
81
78
80
75
43
39
65
59
47
58
78
97
62
59
112
85
85
72
89
113
95
98
97
105
105
87
89
72
103
121
99
132
99
110
92
104
89
85
Hardness
Duro Duro
A 0
57A
Change
points
-1A
OA
-20A
-23A
-9A
-17A
-17A
-19A
+ 1A
+ 3A
-10A
-8A
in
..
. .
Continued
-------
APPENDIX I. (Continued)
ro
OJ
Analytical
Physical properties
properties
Polymer
Polyester
elastomer
Exposure
Liner Time,
no. Waste3 days
75 Unexp.
Slurry oil (W-15) 328
HN03-HF-HOAc (W-9) 323
509
Oil Pond 104 (W-5) 521
1357
Pesticide (W-ll) 501
1258
Pb waste (W-14) 499
1342
Spent caustic (W-2) 526
1237
Thick-
ness,
mil
7
7
7
8
8
9
8
8
7
10
6
7
Vola-
tiles,
%
0.26
0.40
0.39
4.74
1.27
2.59
0.60
2.92
2.63
1.72
0.65
0.89
Extract-
ables,
%
2.74
...
10.77
13.36
7.28
5.15
5.83
2.98
5.35
3.31
Puncture
resistance
Tensi le
strength''
6767 psi
71
33
8
115
89
84
72
88
70
86
88
Elonga-
tion11
575%
77
0.3
4
95
92
96
87
98
90
86
86
S-100h
2585 psi
Retention
77
...
94
85
95
96
88
88
101
109
S-200b
2732 psi
Tear
strength*1
5.92 Ih
Stress
29.9 Ib
E long-
ation
1.30 in.
of properties, %
85
...
100
88
97
94
87
87
101
106
76
24
5
88
105
109
109
89
127
86
107
66
8
2
95
57
90
70
69
75
HI
80
82
14
15
86
63
104
74
87
49
93
76
Hardness
Duro Duro
A D
93A 46D
Change in
points
-10A
-15A
-23A
-10A
-21A
-1A
-15A
-3A
-12A +4D
-?A
-8A
Continued
-------
APPENDIX I. (Continued)
CO
in
Analytical
Physical properties
properties
Exposure
Liner Time,
Polymer no. Waste3 days
Polyvinyl 59 Unexp.
chl oride
Slurry oil (W-15) 327
HFL waste (W-10) 1565
HN03-HF-HOAc (W-9) 505
1352
Oil Pond 104 (W-5) 521
1356
Pesticide (W-ll) 500
1258
Pb waste (W-14) 499
1345
Slop water (W-4) 1565
Spent caustic (W-2) 526
1249
92 Unexp.
D.I. water (W-18) 981
50% Well 118: 985
50% H20 (W-21)
Thick-
ness,
mil
33
33
32
33
32
32
32
32
32
33
34
30
33
32
20
21
19
Vola-
tiles,
%
0.31
0.29
9.90
12.08
13.94
1.70
4.19
2.30
3.61
3.34
4.43
18.72
2.34
1.85
0.06
5.54
3.96
Extract-
ables,
%
35.86
...
34.42
16.68
18.58
32.62
29.99
35.27
33.39
33.47
22.47
10.40
34.62
35.61
32.75
31.77
33.86
Puncture
resistance
Tensile
strength*1
2557 psi
106
101
109
112
113
116
101
109
86
93
93
102
106
2290 psi
110
133
Elonga-
tion*1
375%
90
88
82
71
85
85
101
95
95
93
3
102
97
250%
131
116
S-100b
995 psi
Retention
113
153
200
249
152
174
100
137
82
103
...
99
115
1440 psi
Retention
90
145
S-200b
1580 psi
Tear
strength*1
9.89 Ih
Stress
40.0 Ib
Elong-
ation
0.75 in.
of_properties, %
111
126
147
168
138
145
96
121
82
97
...
96
108
2030 psi
106
123
172
176
126
137
94
114
74
110
30
93
98
8.08 Ih
112
128
122
126
129
150
126
122
110
120
29
104
110
27.4 Ih
in
92
65
59
93
104
137
108
113
125
32
112
113
0.62 in.
of properties , %
89
128
94
143
114
151
94
98
Hardness
f)uro Duro
A D
73A 26(1
Change in
points
-5A
+16A +13D
+11A
+19A +28D
+3A
+7A +90
-3A
+2A
-4A
-6A
+15A +27D
-2A
OA
82A 30D
Change in
points
-3A -3H
+6A +12D
aMatrecon waste serial number given in parentheses.
bAverage of values obtained in machine and transverse directions.
cValue reported is tensile strength of fabric since the bulk of lining material's strength is in the nylon fabric and since the butyl coating over the
fabric did not to fail catastrophically. Fabric failed at 25% elongation.
CValue reported is elongation at ultimate break. Fabric in sheeting retained its original elongation.
eTensile properties determined in accordance with ASTM D751 Method B using 1-in. wide strips for the unexposed sheeting and 0.5-in. wide strips for the
exposed.
-------
APPENDIX J-l
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - NUMBER OF DAYS OF IMMERSION
Ac i d i c
Polymeric membrane
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized poly-
olefin
ro Ethylene propylene
co rubber
Neop rene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvinyl chloride
1 mer
Number
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
"HFL"
(W-10)
250
761
250
761
99
931
250
761
250
761
250
761
250
761
250
761
250
761
250
761
99
934
99
927
99
927
250
761
250
761
250
761
"HN03-
HF-
HOAc"
(W-9)
193
751
193
751
267
1253
193
751
193
751
193
751
193
751
193
751
193
751
193
751
99
1262
99
1255
99
1255
193
751
193
751
193
751
Al kal me
"Slop
water"
(W-4)
193
823
193
823
99
931
193
823
193
823
193
823
193
823
193
823
193
823
193
...
99
934
99
927
99
927
193
823
193
823
193
823
"Spent
caustic"
(W-2)
236
780
236
780
99
1258
238
780
236
780
238
780
236
780
236
780
236
780
236
780
99
1267
99
1266
99
1260
238
780
236
780
236
780
Brine
5%
NaCl
(W-19)
174
1456
174
1456
49
1345
174
1458
174
1456
174
1456
174
1456
174
1456
174
1456
174
1456
93
1360
93
1360
51
1322
174
1456
174
1456
174
1456
Indus-
trial
"Basin
F"
(W-16)
1196
...
1196
67
1288
1195
1196
1196
1195
1196
1196
...
1196
67
1287
67
1287
67
1287
1196
1196
!.
Wastes3
"Lead
waste"b
(W-14)
238
786
238
786
97
1257
236
786
238
786
236
786
238
786
238
786
238
786
238
786
97
1266
97
1259
97
1259
236
786
238
786
238
786
"Slurry
oil"
(W-15)
257
761
257
761
99
784
257
761
257
761
257
761
257
761
257
761
257
761
257
761
99
793
99
786
99
786
257
761
257
761
257
761
Oily
"Oil Pond
104"
(W-5)
248
752
248
752
97
1252
248
752
248
752
248
752
248
752
248
752
248
752
248
752
97
1260
97
1253
97
1253
248
752
248
752
248
752
"Weed
oil"
(W-7)
252
809
252
...
99
1279
252
809
252
809
252
809
252
809
252
809
252
809
252
809
99
1288
99
1287
99
1287
252
809
252
809
252
809
Organic
trace
Sat'dc
TBP
(W-20)
522
1106
522
1112
522
1112
522
1119
522
1119
522
1090
522
1076
522
1076
522
1106
522
1035
522
1070
522
1055
422
1090
522
1035
522
1055
522d
1070d
Pest-
icide
"Weed
killer"
(W-ll)
242
807
242
807
97
1259
242
807
242
807
242
807
242
807
242
807
242
807
242
807
97
1268
97
1267
97
1261
242
807
242
807
242
807
Water
Oeio-
mzed
(W-18)
174
1434
174
1434
49
1323
174
1458
174
1434
174
1434
174
1456
174
1434
174
1434
174
1434
93
1360
93
1322
51
1322
174
1434
174
1434
174
1434
aMatrecon waste serial number shown below identification.
DBlend of three waste streams.
cSaturated solution of tributyl phosphate (TBP) in deionized water.
dLiner Number 89.
-------
APPENDIX J-2
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - DIMENSIONAL CHANGES IN MACHINE AND TRANSVERSE DIRECTIONS3
Ac 1 d i c
Polymeric membrane
liner "HFL"
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfo-
nated poly-
ethy lene
Elasti ci zed
polyolef in
Ethylene
propylene
rubber
r-o
CO
Neoprene
Polyester
elastomer
Polyethylene
High
density
Low
density
Polyp ro-
py lene
Polyvinyl
chloride
No.
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
(W-10)
0.6x0.5
0.3x0.5
0.6x2.0
0x2.2
1.1x0.3
1.0x1.3
1.3x1.7
1.3x1.7
2.3x2.2
2.6x2.9
0.3x0.2
0.3x0
0.7x1.0
0.8x0.5
4.0x4.4
5.1x5.8
2.0x3.4
2.3x3.4
0.3x0.7
0.3x1.0
-O.Sx-0.6
O.Sx-0.6
Ox -0.7
-0.5x0
-0.2x-0.3
-0.3x0
3.3x3.9
4.9x7.1
1.0x1.5
-0.3x0
1.3x2.0
2.0x3.4
"HN03-
HF-
HOAc"
(VI-9)
0.7x0.5
0.3x0.6
0.3x1.7
-0.3x4.4
f
5.6x6.8
0x1.2
2.0x2.4
2.3x2.0
2.5x2.9
0.7x0.7
1.0x0.7
2.0x2.2
0.3x0.2
4.3x5.4
11.5x13.9
2.6x3.4
4.2x5.3
1.0x1.2
piecesS
-0.2x.-0. 6
0x0
-O.Zx-0.3
0x0
0x0
0x0
5.9x6.6
5.6x7.6
-4.3x-3.4
3.0x5.2
5.3x7.4
Alkal me
"Slop
water"
(W-4)
0.3x0.5
0.2x0.2
Oxl.O
0.3x0
-0.2X-0.7
-0.2X-0.3
1.3x1.5
1.3x1.8
1.3x1.5
1.8x2.2
4.3x4.2
4.6x3.5
0.7x0.5
0.7x0.7
1.0x1.2
1.3x1.0
0.3x0.2
4.0x1.0
0.6x0.7
-0.2x0
2.0x0
-O.Zx-0.7
0x0.7
-0.2X-0.3
0.3x0
-5.9x-4.4
-4.3x-3.7
-4.3x-3.4
-6.6X-5.8
-4.9x-2.2
-4.3x-4.2
"Spent
caustic"
(W-2)
0x0
0.3x0
-0.3x0.2
0.3x0.2
-0.2x0
0x0
0.3x0.7
1.0x0.7
0.6x1.0
1.0x1.2
0.7x0.5
0.3x0.4
-0.3x0.2
0.7x0.2
0.3x0
0.7x0.2
0.7x0.5
0.3x0.8
0.7x0
0.7x0.5
-0.2X-0.7
-0.2x0
-0.5X-0.3
0x0
-0.2X-0.3
0x0
0x0
0.3x0
0.3x0.2
0x0.2
0x0
0.3x0.2
Brine
5%
NaCl
(W-19)
0.2x1.0
0x0.7
0.2x-0.3
-0.2X-0.5
0.5x0.6
-0.6X-0.7
l.Oxl.O
0.7x0.7
1.2x2.0
1.7x1.0
Oxl.O
-0.2x0.2
0.5x0
-0.2X-0.3
1.2x1.0
-0.1x0.9
l.Oxl.O
-0.3X-1.4
0.7x0.6
0.4x0.8
Ox-1.0
0x0
Oxl.O
0.2X-0.3
1.0x0
0.5x0
-2.0X-2.0
-2.5X-2.4
-2.0X-2.0
-3.3X-3.4
-0.5X-0.3
-l.lx-1.3
Indus-
trial
"Basin
F"
(W-16)
-0.2x-0.2
0.2x0
0.2x0
-0.2x0
f
1.5x2.0
-O.Zx-0.2
T
-0.2x0.3
0.5x1.0
0.2x0
-O.lx-0.4
0.2x0
-O.lx-1.1
Ox-0.3
0.7x-0.4
-0.2x0.6
0.2x0.3
-0.2x6.8
Wastesb
"Lead
waste"c
(W-14)
7.2x9.8
14.4x11.7
-2.7x30.2
-2.0x45.8
6.8x10.8
16.3x19.6
16.4x22.0
27.2x40.1
13.1x26.6
25.6x40.9
5.2x5.4
6.2x5.2
2.0x5.6
3.0x7.1
10.2x11.0
12.6x13.9
15.8x26.9
20.8x22.1
2.0x4.4
3.1x2.4
1.5x0.6
2.5x1.6
2.0x1.6
4.0x3.3
2.4x0.9
4.5x2.6
1.6x1.2
-2.6x-0.7
2.0x3.4
2.4x5.6
1.3x0.7
-4.4x-0.6
" S 1 u r ry
oil"
(W-15)
5.6x10.2
8.8x10.2
Qxll.O
e
2.7x3.0
28.1x35.3
11.8x8.8
22.0x25.9
15.0x18.0
20.1x33.7
6.5x7.1
7.9x7.8
1.6x2.9
3.3x3.9
8.8x10.5
8.6x9.8
17.1x20.4
35.7x39.5
5.6x5.4
6.6x6.1
0.5x-0.3
3.0x2.0
2.7x2.0
4.7x3.9
-O.Zx-1.2
-0.8x0.3
2.6x3.9
2.6x4.8
2.6x2.4
4.6x6.6
0.7x2.0
-0.3x3.7
Oily
"Oil Pond
104"
(H-5)
27.1x30.2
28.4x32.7
0.6x9.8
0.2x12.4
4.1x4.2
7.5x8.1
16.4x15.6
8.8x9.0
16.7x22.7
14.7x21.5
9.5x9.8
7.5x8.3
3.9x7.3
3.0x4.6
23.4x27.3
23.3x28.0
11.3x10.9
8.6x10.7
2.6x2.7
3.0x2.4
3.4x2.6
2.7x1.6
1.0x1.3
3.1x3.2
-0.2x-0.7
3.3x1.9
-4.9x-4.8
-5.6x-5.8
-0.7X-0.2
-1.3x-0.7
-4.0X-4.2
-4.6x-4.6
"Weed
011"
(W-7)
19.9x22.1
20.0x18.9
-1.6x35.6
f
32.4x37.0
38.6x53.1
38.2x101
35.3x62.0
34.0x106
11.2x12.8
9.7x11.0
9.2x10.3
11.5x19.8
21.7x25.1
21.0x23.2
30.9x32.2
29.9x29.0
6.2x6.4
5.6x5.4
1.9x0.9
3.0x1.6
3.9x3.3
5.9x4.2
3.6x3.3
4.0x2.0
2.6x4.2
4.6x5.4
10.2x12.4
6.4x10.7
2.6x7.6
5.3x10.3
Organi c
trace
Sat'dd
TBP
(W-20)
1.0x0.8
0.5x1.8
6.7x38.3
3.3x46.0
12.6x11.8
14.4x12.6
5.3x7.7
4.6x6.3
11.6x14.3
9.1x11.4
3.2x2.5
2.2x2.0
0.7x2.0
0.7x1.8
1.4x1.8
2.2x2.0
15.5x18.7
13.3x15.2
2.2x2.6
1.0x2.9
0.8x0.6
0.7x0.2
0.5x0
0.2x0.2
1. Ox -0.3
0.1x0.5
17.2x22.3
15.9x19.9
11.3x16.6
10.3x17.3
10. 6x20. Oh
11.3x19.4"
Pest-
icide
"Weed
killer"
(W-ll)
0.6x0.2
0.3x0
0.3x4.9
0.2x3.7
0.2x0.7
1.9x2.3
2.3x3.2
3.0x3.5
4.2x4.4
5.2x5.7
0.3x0.5
0.3x0.2
0.3x1.2
0.3x1.4
2.0x2.4
4.9x5.6
3.0x3.2
3.4x4.2
0.6x1.2
0.7x0.5
-O.Sx-0.3
-0.5x0.7
1.9x-0.6
0.3x0.3
Ox-0.3
0.3x-0.3
1.3x1.2
1.6x1.5
0x0.5
-0.&X-0.7
0.3x1.2
0x0.5
Water
Deio-
nized
(W-18)
Oxl.O
0.2x0.7
l.Oxl.O
3.7x0.7
0.2x0.0
1.7x2.3
2.0x2.0
3.4x2.9
3.0x3.0
7.3x6.3
0x0
-0.5X-0.3
0x0
0.7x1.3
l.Oxl.O
1.0x0.7
2.0x2.0
3.7x2.9
Oxl.O
0x0.3
0x0
0.7X-0.3
0.2x0.3
0.2x0.3
0x0
0x0
Ox-1.0
-1.0x1.3
0x0
-0.2X-1.6
-0.2x0.0
-O.Zx-1.0
Reported values are percent change in machine and transverse directions, respectively. Immersion times for the respective data are presented in
Appendix J-l.
&Matrecon waste serial number shown below identification.
C61end of three wastes.
"^Saturated solution of tributyl phosphate (TBP) in deionized water.
eNot measured due to condition of immersed specimen which had become very tacky and seemed to have partially dissolved.
fNot measured.
SImmersed specimen became brittle and broke in pieces when removed from cell.
hLiner Number 89.
-------
APPENDIX J-3
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - PERCENT INCREASE IN WEIGHT
Percent increase in weight of samples
Ac i d i c
Polymeric membrane
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized poly-
olefin
Ethylene propylene
rubber
ro
U>
oo
Neoprene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvinyl chloride
1 iner
Number
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
"HFL"
(W-10)
2.74
3.71
9.43
12.9
4.2
9.24
6.75
8.95
5.41
7.74
0.25
1.05
3.06
3.05
16.7
23.9
9.60
12.0
0.55
2.03
0.05
0.16
-3.3
0.08
0.05
-0.02
10.2
18.1
2.76
0.86
7.60
14.3
"HN03-
HF-
HOAc"
(W-9)
1.39
3.77
9.31
19.9
2.0
21.2
10.3
10.0
7.46
10.9
2.68
7.57
2.64
4.20
18.3
50.9
10.8
17.4
4.15
6.41
0.1
0.2
-0.3
0.3
0.1
-0.01
16.8
22.1
-2.82
-6.12
19.8
28.2
Al kal me
"Slop
water"
(W-4)
2.04
1.81
1.50
1.89
-0.5
1.83
3.79
7.65
3.84
5.66
17.3
20.7
2.71
3.98
3.13
3.34
0.38
2.66
e
e
0.2
0.52
3.5
1.07
0.1
0.08
-13.5
-11.1
-6.35
-15.7
-13.5
-12.1
"Spent
caustic"
(W-2)
0.37
0.74
0.64
1.11
0.7
0.2
3.32
4.30
2.17
3.28
0.54
0.56
1.34
1.59
0.23
1.30
0.82
1.53
0.64
1.29
0.2
0.01
0.1
0.1
0.2
0.1
0.09
0.43
-3.00
-0.89
0.04
1.08
Brine
5%
NaCl
(W-19)
0.87
1.4
2.54
1.3
0.85
-1.2
5.75
4.06
5.06
5.6
0.09
0.3
2.19
1.0
1.19
1.0
3.54
-0.69
1.5
0.03
0.09
0.07
0.09
-0.11
-0.05
-4.81
-6.2
-4.82
-7.8
-1.51
-1.8
Indus-
trial
"Basi n
F"
(W-16)
1.0
2.0
0.3
1.2
e
5.7
i'.o
e
1.0
3^2
1.2
-0.3
0.1
1.1
0.2
0.7
0.5
i.o
0.7
...
"Lead
waste1'6
(W-14)
20.1
28.7
70.9
119
23.0
29.3
83.0
121
69.6
116
18.2
17.0
23.0
24.8
29.3
34.7
45.6
59.1
7.57
7.40
5.0
4.5
3.1
5.3
6.9
5.9
4.36
-1.54
8.81
7.39
2.22
-5.15
on immersion in different wastes3
"Slurry
oil"
(W-15)
32.3
31.18
59.5
d
11.9
115
51.1
105
53.2
111
21.8
29.4
15.8
19.8
35.3
34.2
60.7
142.6
17.1
16.6
4.4
8.0
8.5
12.0
0.4
1.4
10.7
18.5
11.3
28.9
7.2
14.1
Oi ly
"Oil Pond
104"
(W-5)
97.5
104
31.6
36.9
12.4
20.9
75.10
49.5
58.5
55.0
33.5
28.9
35.4
26.5
80.1
84.7
25.8
26.3
7.90
8.47
3.3
6.6
8.4
10.3
0.6
6.8
-7.65
-10.4
-1.54
-0.54
-10.3
-9.9
"Weed
oil"
(W-7)
70.8
64.2
117
e
118
202
368
211
348
44.2
38.1
73.4
84.4
79.4
76.2
94.8
89.3
16.3
14.7
6.4
7.3
10.7
14.0
1.4
9.1
10.0
14.3
33.4
24.7
18.1
25.2
Orgam c
trace
Sat'dc
TBP
(W-20)
18.1
23.1
117
121
36.2
37.5
31.5
30.1
38.3
31.7
7.9
9.7
6.8
9.8
5.2
5.9
49.4
41.1
4.7
4.6
0.33
0.5
0.44
0.5
0.33
-1.3
57.7
52.8
39.7
40.7
47. 6f
47. 5f
Pest-
icide
"Weed
ki 1 ler"
(W-ll)
0.76
1.57
9.62
12.7
2.8
7.3
13.07
17.26
12.3
15.7
0.00
0.49
3.71
4.51
8.09
20.4
8.54
11.4
2.39
4.15
0.5
0.2
0.2
0.2
0.07
-0.1
4.03
5.13
0.46
0.95
2.89
1.62
Water
Deio-
ni zed
(W-18)
1.34
4.4
5.66
12.4
1.45
7.5
7.99
15.8
7.73
18.9
-0.04
0.6
2.62
3.3
1.93
3.6
7.10
11.4
0.00
-0.4
0.03
0.6
0.03
0.2
-0.01
0.00
0.21
-1.6
1.18
-0.5
0.65
-0.1
Immersion times for the respective data are presented in Appendix J-l.
aMatrecon waste serialnumber shown below identification.
''Blend of three waste streams.
cSaturated solution of tnbutyl phosphate (TBP) in deionized water.
''Not measured because immersed specimen had become very "gooey" and seemed partially dissolved.
eNot measured.
liner Number 89.
-------
APPENDIX J-4
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - PERCENT VOLATILES AFTER IMMERSION
Wastes3
Acidic
Polymeric membrane
1 iner
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized poly-
olefin
Ethylene propylene
ro rubber
CO
to
Neoprene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvinyl chloride
No.
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
Original
values
0.46
0.14
0.66
0.51
0.42
0.15
0.31
0.34
0.37
0.26
0.14
0.18
0.01
0.15
0.31
0.17
"HFL"
(W-10)
1.91
2.95
6.87
8.47
5.50
7.40
4.79
8.01
4.98
6.91
0.70
1.93
2.49
3.22
15.52
19.59
8.71
10.88
0.12
2.11
0.02
0.21
0.03
0.25
0.12
0.36
10.43
17.30
3.89
3.00
7.38
13.32
"HN03-
HF-
HOAc"
(W-9)
2.41
3.85
12.52
20.42
d
18.70
2.61
10.42
8.54
9.14
3.19
7.21
6.67
3.09
16.23
22.55
12.27
13.67
1.36
2.83
0.34
d
0.04
d
0.35
d
16.20
22.61
11.68
10.58
21.39
23.18
Alkal ine
"Slop
water"
(W-4)
1.32
1.24
2.36
5.50
2.96
6.91
7.46
6.53
1.98
5.96
10.88
11.37
3.47
4.41
2.95
2.97
8.96
9.70
2.06
...
0.19
0.36
0.41
0.42
0.11
0.28
11.03
13.36
2.41
7.84
16.96
13.59
"Spent
caustic"
(W-2)
0.67
0.71
1.46
1.60
2.42
2.63
3.67
4.20
2.73
3.62
0.72
0.58
1.43
2.16
0.90
1.22
2.90
2.93
0.39
1.27
0.09
d
0.03
d
0.11
d
0.44
0.56
1.06
1.49
0.89
1.21
Brine
5%
NaCl
(W-19)
d
2.40
d
3.30
d
2.80
d
6.20
d
6.40
d
0.60
d
3.20
d
2.50
d
4.90
d
0.60
d
0.01
d
0.10
d
0.20
d
2.10
d
2.30
d
2.40
Indus-
trial
"Basin
F"
(W-16)
...
1.60
3'.20
d
2.80
...
6.40
...
6.50
0^90
...
3.80
« .
2.60
...
5.20
...
1.30
d
d
d
d
d
0.07
...
4.00
o!o4
...
"Lead
waste"b
(W-14)
3.67
15.34
23.62
42.24
15.01
18.20
17.86
33.01
13.09
24.40
2.04
9.46
4.59
13.89
6.48
18.47
14.48
23.63
1.15
5.77
1.76
d
1.09
d
3.27
d
4.74
16.14
2.93
12.73
3.61
11.53
"Slurry
oil"
(W-15)
1.13
3.29
0.59
e
3.77
2.90
0.54
6.05
0.72
4.82
0.54
1.50
0.96
4.36
0.86
4.20
0.74
3.90
0.60
3.40
1.00
0.60
1.67
0.80
0.25
0.50
0.53
3.62
0.56
4.56
0.59
3.50
Oily
"Oil Pond
104"
(W-5)
2.99
9.78
6.90
5.22
9.56
13.00
10.79
20.22
11.07
9.98
1.80
3.07
4.06
8.54
18.35
11.76
9.03
6.26
1.46
2.11
3.74
d
2.07
d
0.40
d
2.19
2.69
1.47
3.26
2.11
4.33
"Weed
oil"
(W-7)
14.47
19.14
23.04
63.15
57.80
31.52
50.74
18.71
39.71
14.24
16.37
6.29
24.09
30.88
33.37
35.39
28.89
9.98
9.48
4.60
d
4.84
d
0.83
d
17.07
17.14
20.98
16.13
23.34
24.07
Organic
trace
Sat'dC
TBP
(W-20)
2.68
5.20
42.29
56.60
20.33
29.00
20.51
21.60
21.13
23.10
2.22
6.50
6.11
8.40
4.65
6.60
25.14
29.70
4.38
5.60
d
0.50
d
0.50
0.01
0.30
14.80
35.10
12.12
30.60
23.33f
24.30f
Pest-
icide
"Weed
killer"
(W-ll)
1.14
3.04
7.77
8.63
3.79
9.37
9.00
10.79
8.75
7.94
0.28
0.45
2.99
4.89
6.17
15.61
7.04
7.26
0.48
1.75
0.12
d
0.14
d
0.15
d
1.59
3.09
2.58
4.01
2.61
3.53
Water
Deio-
nized
(W-18)
d
4.30
d
11.30
d
9.30
d
13.20
d
15.80
d
0.50
d
5.50
d
4.00
d
12.40
d
0.40
d
1.10
d
0.07
d
0.24
d
2.50
d
3.30
d
2.90
aMatrecon waste serial number shown below identification.
^Blend of three waste streams.
cSaturated solution of tributyl phosphate (TBP) in deiomzed water.
^Not measured.
eNot measured because of condition of specimen.
'Liner Number 89. Original value = 0.03%.
Immersion times for the respective data are presented in Appendix J-l.
-------
APPENDIX J-5
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - PERCENT EXTRACTABLES AFTER IMMERSION
Ac i d i c
"HN03- Alkaline
Polymeric membrane
1 1 ner
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized poly-
olefin
Ethylene propylene
rubber
Neoprene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvinyl chloride
TJo.
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
Original
values
11.79
9.13
17.42
3.77
4.08
5.50
18.16
23.64
21.46
2.74
2.07
33.90
35.86
33.46
HF- "Slop
"HFL" HOAc" water"
(W-10) (W-9) (W-4)
10.62 11.07 12.81
10.19 12.04 6.45
16.70 18.70 15.37
3.77 s!?5 3!63
3.64 3.96 3.70
5.07 6.22 2.96
i7a2 i?!63 isii?
22.43 25.36 24.70
19!58 19J8 \7'.63
3.28 10.77
0.97 ... 0.53
I'M ::: 2'.9\
0.74 ... 0.69
32.25 1.34
33!% 23^5 14.70
... 33\20 2.15
"Spent
caustic"
(W-2)
10.87
9.18
18.01
3'.83
4.16
5.46
18:62
22.89
20:83
2.71
...
...
...
33.89
35.81
32 '.53
Wastes3
Indus-
Brine trial Oily
5% "Basin "Lead "Slurry "Oil Pond
NaCl F" waste"b oil" 104"
(W-19) (W-16) (W-14) (W-15) (W-5)
31.17
17.08 27.23 40.34
16.57
16.62 ... 19.18
57.48 16.09
25.93
4.56 45.43 16.34
17.02
3.74 59.81 15.92
18.60
6.86 23.31 17.78
19.60
20.74 27.34 22.24
31.63
29.99 38.35 43.45
25.32
19.21 58.47 23.85
3.25 16.64 6.54
!!! ... ... siss s'.is
... ... ... 8.25 2.49
... ... ... 1.20 7.67
50.43
40.55 17.95
55.56
35.81 47.56 27.95
20.74
38.49 14.81
"Weed
oil"
(W-7)
15.16
36.48
19.01
16.08
8.08
is.'es
25^3
7.60
6:i6
uso
4.70
1.41
23.84
sues
21.52
Organic Pest-
trace icide Water
Sat'dc "Weed Deio-
TBP killer" nized
(W-20) (W-ll) (W-18)
12.26
11.89 11.03
5.71
26.1 9.07
15.24
16.82 15.86
3.60
3.67 3.68
3.97
4.35 4.50
6.29
6.70 6.00
16.74
18.81 17.69
22.11
23.41 24.71
16.85
21.46 20.52
3.25
3.39
0.81
2.67
3.94
1.44
23.78
33.28 35.38 31.75
26.14
51.66 35.90 35.20
24.90d
25.84d 31.71
aHatrecon waste serial number shown below identification. Immersion time for the respective
in accordance with Matrecon Test Method 2 (Matrecon, 1983, pp. 340-43).
^Blend of three waste streams.
cSaturated solution of tributyl phosphate (TBP) in deionized water.
dLiner Number 89. Original value = 25.17%.
data are presented in Appendix J-l. Extractables determinec
-------
APPENDIX J-6
EXPOSURE OF LINER SPECIMENS IN IMMERSION TEST - RETENTION OF STRESS AT 100* ELONGATION
Retention of original property on immersion in different
Acidic
Polymeric membrane liner
Polymer
Butyl rubber
Chlorinated
polyethylene
Chlorosulfonated
polyethylene
Elasticized polyolefin
Ethyl ene propylene
rubber
Neoprene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvinyl chloride
Number
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
On gi nal
valueb,
psi
308
900
618
938
880
923
760
338
558
2585
2510
2583J
1320
1210J
k
3038J
1420
995
1735
"HFL"
(W-10)
84
93
98
117
93
79
98
126
91
110
97
105
92
116
86
100
82
104
98
117
101
891
97
1011
k
101'
83
95
99
124
70
83
"HN03-
HF-
HOAc"
(H-9)
70
88
92
129
9
45
81
68
100
71
99
93
107
88
75
58
83
62
80
n
103
791
99
105'
k
98'
84
93
199
252
68
70
Alkal me
"Slop
water"
(W-4)
85
89
113
130
96
110
149
180
119
169
82
93
69
63
88
107
96
115
90
9
h
90'
97
98'
k
981
196
206
161
239
183
m
"Spent
caustic"
(W-2)
81
91
115
126
88
119
150
171
130
164
95
109
90
107
93
100
97
121
94
104
101
95i
100
991
k
106'
103
110
103
123
86
99
Brine
5%
NaCl
(W-19)
103
89
124
152
91
121
115
g
104
134
102
114
104
9
85
99
106
144
109
114
h
1041
104
103'
k
105'
116
139
136
185
96
125
Indus-
trial
"Basin
F"
(W-16)
...
76
126
103
85
...
9
...
152
119
. . .
g
104
93
103
h
83'
100
102'
k
102'
95
106
"Lead
waste"0
(W-14)
59
57
37
18
67
44
98
89
79
91
80
76
60
47
83
73
50
38
91
91
100
82'
95
93'
k
95'
82
91
89
87
83
95
"Slurry
oil"
(W-15)
66
55
44
f
74
49
90
73
96
85
70
72
63
61
65
60
58
40
79
75
99
86'
91
100'
k
108'
89
118
114
107
99
122
Oily
"Oil Pond
104"
(W-5)
44
45
44
48
62
77
49
88
58
85
62
75
38
57
66
58
46
70
82
95
102
88'
92
90'
k
100'
168
186
118
145
145
172
wastes3, %
"Weed
oil"
(W-7)
36-47*
38
8
24
28
7-46^
f
34
f
55-59^
54
28
f
59-64e
67
25-26e
27
68-69e
77
98
83'
88
89'
k
97'
48- 70^
46
32-35^
45
37-41e
45
Organic
trace
Sat'dd
TBP
(W-20)
79
60
6
9
48
55
g
g
80
106
71
87
9
9
82
89
37
38
90
90
92i
89'
104J
103'
109'
107'
15
18
27
28
23'
25l
Pest-
icide
"Weed
killer"
(W-ll)
78
89
102
103
76
136
109
124
102
120
108
116
98
100
85
89
84
109
99
110
100
83'
94
100'
k
99'
99
106
118
130
83
99
Water
Deio-
mzed
(W-18)
90
89
129
123
125
108
142
g
143
106
123
104
118
9
109
93
126
109
117
105
h
98'
HI.
105'
k
108'
111
108
113
116
100
104
dMatrecon waste serial number shown below identification. Immersion times for the respective data are given in Appendix J-l.
°Average of values in machine and transverse directions of specimens tested in accordance with ASTM D412 or D638 at 20 in. per minute unless otherwise noted.
C81end of three waste streams.
^Saturated solution of tributyl phosphate (TBP) in deionized water.
^aste stratified into an aqueous and an oily phase. Reported value ranges indicate the different effects of the two phases.
^Not measured because of condition of immersed specimen.
9Not measured.
"Immersed sample failed at less than 100% elongation.
'Retention of values obtained for specimens tested at 2 in. per minute.
JAverage of values in machine and transverse directions of specimens tested at 2 in. per minute.
^Unexposed material failed at less than 100% elongation when tested at 20 in. per minute.
'Liner Number 89. Original value = 1688 psi.
Transverse direction failed at 80% elongation.
-------
APPENDIX ,1-7
EXPOSURE OF LINED SPECIMENS IN IMMERSION TEST - RETENTION OF ELONGATION AT BREAK
Retention of original property on Inversion in different wastes3. I
Acidic
Polymeric membrane
Polymer
Butyl rubber
Chlorinated
polyethyl ene
Chlorosulfonated
polyethylene
Elastidzed poly-
olefln
Ethylene propylene
rubber
Neoprene
Polyester elastomer
Polyethylene
High density
Low density
Polypropylene
Polyvlnyl chloride
liner
Number
44
77
100
6R
55
36
83R
91
90
75
105
108
106
11
59
88
Original
value11,
I
443
403
403
243
280
665
253
488
415
575
113
843'
555
5251
58
653<
358
375
330
"HFL"
(W-10)
109
93
93
79
67
77
106
89
111
93
108
95
144
109
98
87
98
68
97
90
92
102h
99
9!)h
91
95"
91
83
103
95
108
87
"HN03-
HF-
HOAc"
(W-9)
109
110
87
77
g
92
137
121
83
104
102
96
109
136
104
97
86
87
46
1
130
17"
100
86"
140
92"
87
84
82
67
91
86
Alkal ine
"Slop
water"
(W-4)
103
100
88
83
90
73
62
54
71
64
84
100
147
147
98
93
82
81
86
g
86
99h
99
90"
91
98"
58
35
91
57
33
35
"Spent
caustic"
(H-2)
98
93
95
86
92
77
89
69
75
73
97
90
107
105
107
106
98
83
96
83
100
44"
103
89"
91
94h
102
95
102
89
108
100
Brine
5%
NaCl
(W-19)
98
102
65
75
91
87
93
9
94
82
100
95
121
9
103
102
83
76
89
85
78
62"
99
96"
132
97"
101
87
100
80
97
81
I ndus-
trlal
"Basin
F"
(W-16)
104
77
84
87
. . .
9
73
"93
9
100
'so
~86
74
108
89"
47
76"
94
90
"Lead
waste"c
(H-14)
115
111
87
89
94
87
72
62
81
60
89
84
134
156
92
98
97
91
102
101
129
82"
105
67"
942
108"
101
101
106
103
108
104
"Slurry
oil"
(H-15)
93
101
97
f
102
58
81
74
65
51
96
89
134
146
92
100
77
62
94
87
134
92"
95
93"
82
112"
92
74
92
80
85
82
Oily
Organ) c
trace
"Oil Pond "Weed
104" oil"
(W-5) (W-7)
52
54
100
93
100
72
70
76
79
69
86
88
154
133
47
52
98
77
98
96
196
79h
96
66"
204
104"
87
83
98
98
78
78
43-100e
71
42
51
40
83
9
82
f
63-77e
78
124
f
45-53e
56
47-70e
64
96-99e
96
125
87"
86
48"
270
107"
99-1036
105
104-1116
98
112-114?
107
Pest-
icide
Sat'dd "Heed
TBP killer"
(W-20) (W-ll)
109
109
154
139
78
78
9
9
79
73
73
70
g
9
106
103
82
88
101
96
100"
42h
102"
82"
104"
92"
103
99
91
96
11U
105J
98
109
96
92
101
67
97
78
101
79
101
95
120
126
109
101
96
86
96
89
113
43"
107
87"
168
94"
104
101
101
98
95
98
Water
Oeio-
n i 2 ed
(W-18)
100
99
7;
68
81
73
82-
g
79
87
93
97
101
9
105
100
75
74
83
93
53
91"
101
88"
207
94"
105
90
97
89
102
89
"Matrecon waste serial number shown below identification. Inmersion trmes for the respective data are presented in Appendix J-l.
Average of values 1n machine and transverse directions of specimens tested in accordance with ASTM 0412 or 0638 at 20 in. per minute unless otherwise noted.
cBlend of three waste streams.
dSaturated solution of tributyl phosphate (TBP) In defonlzed water.
eWaste stratified into an aqueous phase and an oily phase. Reported value ranges indicate the different effects of the two phases.
^Not measured because of condition of specimen.
9Not measured.
"Retention of values obtained for specimens tested at 2 in. per minute.
'Average of values in machine and transverse directions tested at 2 in. per minute.
JLiner Number 89. Original value * 320%.
-------
ro
-^
co
APPENDIX K
EFFECT ON THE PROPERTIES3 OF POLYMERIC MEMBRANE LINING MATERIALS
OF EXPOSURE ON ROOF OF LABORATORY IN OAKLAND, CALIFORNIA
Polymer
Compound type^
Fabric, type
Thread count, epi
Nominal thickness, mils
Liner number^
Exposure time, days
Weight, % change
Area, % change
Extractables, %
Volatiles, %
Tensile at fabric break
Tensile at ultimate break
Elongation at break
S-100
S-200
Tear strength (Die C)
Butyl
XL
Nylon
22 x llc
34
57R
343
-1.89 -2
-1.65 -1
6.36 6.47 5
0.29 0.26 0
Percent
72.7 ppi 1146
e
42% 1256
... ...
745
.79
.31
.99
.31
Chi
1231
-3
-1
5
0
.32
.29
.71
.30
9
0
.13
.14
retention
102
116
»
2198 psi
119
. . .
102
. . .
403%
900 psi
1180 psi
...
Change i
#
n poi
nts
...
7
.38 Ib
orinated polyethylene
TP
*29
77
343
-0.99
-7.19
8.22
0.17
-2
-6
5
0
Percent
...
110e
1006
1156
1146
986
Change
745
.27
.87
.99
.19
1231
-3
-7
6
0
retenti
. . .
98
84
136
129
104d
.15
.33
.32
.33
on
*
97
81
139
135
116
in points
Hardness
71A
+1A
-1A
-2A
80A
+4A
+2A
+4A
Continued
-------
APPENDIX K. (Continued)
Polymer
Compound type*3
Fabric, type
Thread count, epi
Nominal thickness, mils
Liner number^
Exposure time, days
Weight, % change
Area, % change
Extractables, %
Volatiles, %
Tensile at fabric break
Tensile at ultimate break
Elongation at break
S-100
S-200
Tear strength (Die C)
Hardness
Chlorosulfonated polyethylene
TP
Nylon
8x8
31
*
3.77
0.51
35.85 ppi
1728 psi
243%
938 psi
1550 psi
77A
6R
343
0.64 0
-7.38 -6
2.93 2
0.88 1
Percent
125e
153e
6ie
199e
Change
-OA
745 1231
.91 1.80
.15 -6.04
.72 3.32
.19 2.57
retention
135 139
151 161
52 52
232 248
*
in points
-1A -3A
El
*
5.50
0.15
2620 psi
665%
932 psi
1018 psi
8.56 Ib
89A
32D
asticized polyolefin
CX
*
22
36
343
-0.72 -1
-1.94 -1
5.89 5
0.12 0
Percent
gge
966
1096
1096
1076
Change
+OA
745 1231
.55 -1.93
.31 -1.38
.87 5.33
.10 0 06
retention
93 96
96 95
107 119
107 116
109e 98
in points
-2A +OA
+6D
Continued
-------
rv>
-p»
tn
APPENDIX K. (Continued)
Polymer
Compound type*5
Fabric, type
Thread count, epi
Nominal thickness, mils
Liner numberc
Exposure time, days
Weight, % change
Area, % change
Extractables, %
Volatiles, %
Tensile at fabric break
Tensile at ultimate break
Elongation at break
S-100
S-200
Tear strength (Die C)
Ethyl ene propyl
XL
62.5
23.41
0.38
1593 psi
510%
335 psi
770 psi
12.75 Ib
8
343
-2.02 -3
-2.58 -2
22.36 20
0.36 0
Percent
1096
946
123e
119e
966
Change in
ene rubber
745
.09
.61
.90
.34
Ethyl ene propyl
XL
*
30
1231
-3
-3
21
0
.91
.25
.31
.45
»
22.96
0.50
retention
106
91
127
121
996
*
113
91
142
131
96
1900 psi
450%
358 psi
878 psi
7.40 Ib
points
26
343
-1.69 -2
-0.96 -1
21.88 21
0.45 0
Percent
1006
896
1046
1106
906
Change i
ene rubber
745
.71
.61
.20
.48
1231
-3
-2
21
0
.11
.87
.75
.62
retention
»
104
92
113
117
966
108
94
119
121
87
n points
Hardness
58A
+5A
+5A
+7A
58A
+OA
+2A
+3A
Continued
-------
Ol
APPENDIX K. (Continued)
Polymer
Compound type^
Fabric, type
Thread count, epi
Nominal thickness, mils
Li ner number^
Exposure time, days
Weight, % change
Area, % change
Extractables, %
Volatiles, %
Tensile at fabric break
Tensile at ultimate break
Elongation at break
S-100
S-200
Tear strength (Die C)
13.69
0.45
1785 psi
320%
460 psi
1038 psi
5.41 Ib
Neoprene
XL
34
43
343 745 1231
-1.86 -2.96 -3.11
-2.29 -1.96 -3.86
11.71 10.98 9.93
0.66 0.79 1.03
Percent retention
94e 88 88
766 70 63
146e 170 184
135^ 144 149
8Qe 86e 86
Change in points
*
13.43
0.19
1755 psi
400%
383 psi
790 psi
11.13 Ib
Neoprene
XL
60
82
343
-0.53 -1
-1.32 -1
11.97 12
0.47 0
Percent
95e
796
140e
134e
84e
Change
745 1231
.17 -1.31
.31 -2.32
.05 11.45
.53 0.76
retention
*
93 92
66 63
175 188
159 168
87e 82
in points
Hardness
57A
+10A
+11A
+14A
57A
+8A
+9A
+12A
Continued
-------
APPENDIX K. (Continued)
ro
Polymer
Compound type^
Fabric, type
Thread count, epi
Nominal thickness, mils
Liner number^
Exposure time, days
Weight, % change
Area, % change
Extractables, %
Volatiles, %
Tensile at fabric break
Tensile at ultimate break
Elongation at break
S-100
S-200
Tear strength (Die C)
Hardness
Polyester
CX
75
...
...
2.74
0.26
6768 psi
575%
2585 psi
2733 psi
5.92 Ib
93A
45D
343
-2.50 -8
-1.29 -1
9 3
0.35 0
Percent
75e
89e
1046
1006
896
Change
-6A
...
745
.32
.00
.42
.12
1231
-6.23
-1.42
3.92
0.13
Polyvinyl chloride
TP
'36
11
...
...
33.90
0.15
retention
66
84
107
103
70
83
110
107
896 103
in
-1A
...
points
-1A
+7D
2878 psi
357%
1420 psi
2013 psi
11.20 Ib
80A
...
343
-1.36 -8
-2.90 -6
33.86 30
0.18 0
Percent
966
1006
1076
100e
976
Change
+OA
...
745
.40
.09
.33
.45
1231
-15.61
-10.28
26.27
0.42
Polyvinyl chloride
TP
59
...
...
...
35.86
0.31
retention
96
91
127
111
97
77
161
128
1236 134
in
+2A
...
points
+7A
...
2558 psi
375%
995 psi
1580 psi
9.89 Ib
343
-1.45
-3.92
34.94
0.17
745 1231
-6.66 -10.31
-7.39 -10.75
30.31 27.78
0.23 0.13
Percent retention
...
966
966
1236
107e
1026
107 111
93 86
161 185
132 145
1356 144
Change in points
73A
26n
+3A
...
+10A +13A
+130
aExtractable content measured in accordance with ASTM D3421, modified so as to allow for suitable solvent of polymer type;
volatile content is percent loss in weight after 2 hours at 105°C; tensile values measured in accordance with ASTM D412 and D638,
using a small tabend dumbbell with a 0.25 in. neck and tested at 20 ipm. Tear strength measured in accordance with ASTM 0624.
Reported values for both tensile and tear are average of machine and transverse directions except where otherwise noted. Hardness
measured in accordance with ASTM D2240.
bXL = crosslinked or vulcanized; TP = thermoplastic; CX = crystalline.
cThread count in the machine and transverse directions, respectively.
^Matrecon liner serial number; R = fabric reinforced.
eRetention of machine direction only.
fBulk of lining material's strength is in the nylon fabric. The butyl coating over the fabric tended not to fail catastrophi-
cally, and no useful value could be obtained for tensile at ultimate break.
SExtractable content not determined because of lack of material.
-------
APPENDIX L
VOLATILES TEST OF UNEXPOSED POLYMERIC LINING MATERIALS
(Matrecon Test Method 1 - October 1982)
This test is to be performed on unexposed membrane liner materials.
Significance
This test can be used to determine the volatile content of an unex-
posed sheeting, including water, volatile oils, and solvents. Nonvolatile
dissolved or absorbed components of a specimen will be determined by the
extractables test which is run after the volatiles have been removed (see
Matrecon Test Method 2). The volatile content should be determined as soon
as possible after the liner has been received. By identifying the orienta-
tion of the disk with respect to the sheeting at the time it was died out,
the grain of the sheeting can be established.
Definitions
Volatiles are the fraction of weight lost by a specimen during the
specified heating process described below.
Apparatus
- Two-inch interior diameter circular die.
- Analytical balance.
- Air-oven.
Test Specimen
Two-inch diameter disks died out of the sheeting, as received.
Number of Test Specimens
All determinations should be run in duplicate.
Procedure
1. Draw a line on the sheeting to mark "grain" or machine direction.
If the "grain" is unknown, draw a random straight line on the
sheeting.
248
-------
2. Die out a 2-in. diameter disk so that the lines fall approximately
in the middle of the specimen.
3. Weigh specimen in tared, closed container to the nearest 0.0001 g.
Record weight "as received weight."
4. Dry specimen out on Teflon screen for two hours at 105+2°C.
5. Cool in desiccator for 20 minutes.
6. Weigh on analytical balance to 0.0001 g; record as the "oven dry
weight."
7. Measure diameters in machine and transverse directions. Record
to 0.001 inches.
8. If machine direction is unknown, find and record largest and
smallest diameters of disk. Mark small diameter as machine
direction on disk as shown in Figure L-l. Use the dried disk to
determine the orientation of the sheeting from which it was
removed.
Oven Dry
As Received
Figure L-l. Machine direction determination.
9. Retain specimens for additional testing, e.g. specific gravity,
thermogravimetry, extractables, etc.
249
-------
Calculations
Calculate the percent volatiles as follows:
Volatiles, % = C(A-B)/A] x 100
where:
A = grans of specimen, "as received weight"
B = grams of specimen, "oven dry weight"
Report
1. Identification of sheeting.
2. Result of above calculation of volatiles.
250
-------
APPENDIX M
TEST FOR THE EXTRACTABLE CONTENT OF UNEXPOSED LINING MATERIALS
(Matrecon Test Method 2 - October 1982)
This procedure covers the extraction of plasticizers, oils, and
other solvent-soluble constituents of polymeric lining materials with a
solvent that neither decomposes nor dissolves the polymer.
References
This procedure generally follows ASTM D3421, "Extraction and Analysis
of Plasticizers Mixtures from Vinyl Chloride Plastics". See also ASTM
D297, "Rubber Products-Chemical Analysis," Paragraphs 16-18.
Significance
The extractable content of a polymeric lining material can consist of
plasticizers, oils, or other solvent-soluble constituents that impart or
help maintain specific properties such as flexibility and processability.
During exposure to a waste, the extractables content may be extracted out
by the waste resulting in a change in properties. Another possibility is
that during exposure the material could absorb nonvolatilizable, in additon
to volatile, constituents from a waste. Measuring the extractable content
of unexposed lining materials is, therefore, useful for monitoring the
effect of an exposure on a lining material. The extract and the extracted
liner obtained by this procedure can be used for further analytical test-
ing, e.g. gas chromatography, infrared, ash, thermogravimetry, etc. for
fingerprinting the liner.
Apparatus
- Aluminum weighing dishes.
- Analytical balance.
- Air-oven.
- Soxhlet extractor (or rubber extraction apparatus).
- Extraction thimbles.
251
-------
- 500 ml flat-bottomed flask (or 400 ml thin-walled Erlenmeyer
flask if rubber extraction apparatus is used).
- Hot plate or steam plate.
- Boiling beads.
- Cotton wool.
- Alumi num foil.
Note: The rubber extraction apparatus may be substituted for the
Soxhlet with all polymers except PVC and CPE. An appropriate
reduction in sample size and solvent volume must be made.
The metal condensers of the rubber extraction apparatus are
corroded by HC1 which is produced during extraction of the PVC
and CPE.
Reagents
Table M-l lists the recommended solvents for the extraction of mem-
brane liners of each polymer type.
TABLE M-l. SOLVENTS FOR EXTRACTION OF POLYMERIC MEMBRANES
Polymer type
Extraction solvent
Butyl rubber (IIR)
Chlorinated polyethylene (CPE)
Chlorosulfonated polyethylene (CSPE)
Elasticized polyolefin
Epichlorhydrin rubber (CO and ECO)
Ethylene propylene rubber (EPDM)
Neoprene
Nitrile rubber (vulcanized)
Nitrile-modified polyvinyl chloride
Polyester elastomer
High-density polyethylene (HOPE)
Polyvinyl chloride (PVC)
Thermoplastic olefinic elastomer
Methyl ethyl ketone
n-Heptane
Acetone
Methyl ethyl ketone
Methyl ethyl ketone or acetone
Methyl ethyl ketone
Acetone
Acetone
2:1 blend of carbon tetrachlo-
ride and methyl alcohol
Methyl ethyl ketone
Methyl ethyl ketone
2:1 blend of carbon tetrachlo-
ride and methyl alcohol
Methyl ethyl ketone
Note: Because lining materials can be sheetings based on polymeric
alloys which are marketed under a trade name or under the name
of only one of polymers, this list can only be taken as a
guideline for choosing a suitable solvent for determining the
extractables. Once a suitable solvent has been found, it is
important that the same solvent be used for determining the
extractables across the range of exposure periods.
252
-------
Sample size
If using the Soxhlet extractor, about five grams of devolati1ized
material are needed per extraction. If using the rubber extraction ap-
paratus, about two grams are needed. All extractions should be run in
duplicate.
Procedure
1. Cut the sample into cubes no larger than 0.25 in. on a side.
2. Weigh sample into an aluminum weighing dish and dry in moving air at
room temperature for more than 16 hours.
3. Place in air-oven for two hours at 105+2°C. Weigh the sample.
4. Weigh the sample into a tared extraction thimble. Plug small
thimbles with a piece of cotton wool to prevent the pieces from
floating out of the thimble. (Large thimbles are tall enough to
stay above the level of the liquid.)
5a. For PVC and CPE materials: Add 200 ml of extraction solvent to the
500 mL flat-bottom distillation flask. Add boiling beads to reduce
bumping.
5b. For other materials: Dry and preweigh a thin-walled Erlenmeyer
distillation flask. Add 200 mL of extraction solvent to the
flask.
6. Place the thimble in the extractor barrel, put the condenser in
place, and run the extraction a minimum of 22 hours. Aluminum
foil can be wrapped around the extractor and flask to increase the
distillation rate.
7a. por pvc an(j cp£ materials: When the extraction is complete, rinse
all the solvent from the extractor barrel into the distillation
flask. Decant the solvent from the flask into a dried, tared 500
mL Erlenmeyer flask and then evaporate on a steam bath with fil-
tered air. Place the flask in an oven at 70±2°C and dry two
hours. Hold the extract for further testing e.g. gas chromato-
graphy and infrared.
7b. For other materials: When the extraction is complete, rinse all the
solvent from the extractor barrel into the distillation flask.
Evaporate the solvent from the flask on a steam bath with filtered
air. Place the flask in an oven at 70+2°C and dry two hours.
Hold the extract for further testing.
8. If the extract contains constituents which may volatilize during
the evaporation procedure or is to be used for further analysis,
heat the flask with extract in solution on a 70°C hot plate or a
steam plate to near dryness. Complete evaporation of solvent in
vacuum oven at 40°C.
253
-------
9. Remove extracted liner from the thimble after excess solvent is
removed and place in a tared aluminum weighing dish. Heat to
constant weight at 105°C. Extracted PVC specimens cannot be dried
to a constant weight at 105°C when they are extracted with a blend
of CC14 and C^OH because, once the stabilizer additives have
been removed by extraction, the polymer undergoes slow decomposi-
tion with HC1 loss. It is recommended that the sample be dried 72
hours at 105°C. Hold the extracted liner for further testing.
Note: In cases where the extracted specimen sticks to the
extraction thimble, the extraction thimble should be
dried to constant weight at 70°C before the extraction
and the weight recorded as the true weight of the
thimble. After the extraction, the extracted liner can
be dried to a constant weight in the thimble.
Calculations
Calculate the percent volatiles as follows:
Volatiles, % = [(A-B)/A] x 100
where:
A = grams of specimen, as received
B = grams of specimen after 2 hours at 105°C
Calculate the percent extractables as follows:
Extractables, % = (B/A) x 100
where:
A = grams of specimen
B = grams of dried extract
Note: In cases where the extract may contain some constituents
which volatilized while the extraction solvent was evapor-
ated, the percent extractables should also be calculated
as follows:
Extractables based on loss from specimen, % = [(A-B)/A]
where:
A = grams of specimen
B = grams of extracted liner
Report
1. Identification of sheeting.
2. Extraction solvent.
3. Volatiles.
4. Extractables.
5. Extractables based on loss from specimen, if calculated.
254
-------
APPENDIX N
PROCEDURE FOR THE ANALYSIS OF UNEXPOSED
POLYMERIC MEMBRANES BY PYROLYSIS
Apparatus
1. Dry and oxygen-free N2 gas.
2. Ai r or oxygen.
3. Size 00 000 pyrolysis boat.
4. Quartz or Vycor tube.
5. Rotameter with a flow capacity of at least 500 mL/minute.
6. Thermocouple and read-out usable at 500 - 600°C.
7. Bunsen burner.
Procedure
1. Heat clean size 00 000 pyrolysis boats at 600°C for 10 minutes to
drive off contamination.
2. After cooling, weigh the boats (about 0.4 g each) to the nearest
0.0001 g.
3. Place 0.02 to 0.04 g of sample cut with a razor blade into the
boat. Keep the volume small to reduce boil out.
4. Flush a hooded Vycor tube with dry, oxygen-free nitrogen at about
500 mL/mi nute.
5. Set a medium hot Bunsen burner about 2-3 in. below the tube and
adjust the heat until a thermocouple in the center of the tube
registers 500 - 550°C.
6. Insert the boat in the tube end opposite the flow and push slowly
to about 1-2 in. from the hot zone. Advance sample cautiously
allowing boiling and gas evolution to begin slowly. Nearly all
gas evolution should be complete before final insertion into the
hot zone.
7. Heat at 500 - 550°C for at least 5 minutes after all visible
changes are complete.
255
-------
8. Push sample out of hot zone and allow to cool in the nitrogen
stream.
9. Weigh and record on data sheet.
10. Flush the tube with 02 at 500 nt/min and insert sample directly
into the 500 - 550°C hot zone. The sample should remain until all
visible black is gone and the sample is at least gray in color (it
will often be white).
11. Cool the sample in the gas stream and reweigh.
12. Calculate the composition as indicated in the sample calculation.
13. Two samples should be run. If results are not within 2% of each
other, run two more samples.
14. Boats which will not burn clean may be treated with warm, con-
centrated nitric acid, rinsed with water, and then brushed to
remove residues. Boats should be heated to pyrolysis temperature
before reweighing for use.
Sample Calculation
The data given are for a PVC compound. All values are the average of two
determi nations.
Data:
A = % loss on pyrolysis at 550°C under N2 = 81.3
B = % further loss on pyrolysis at 550°C under 02 = 11.2
C = % loss on solvent extraction = 33.9
D = % carbonaceous residue {from Table below) = 4.9
Calculations:
Organic polymer = (A+D-C) = 52.3%
Monomeric organic additives (extractables) = C = 33.9%
Carbon black = (B-D) = 6.3%
Inorganic filler (ash) = (100-A-B) = 7.5%
Total 100%
TABLE N-l. CARBONACEOUS RESIDUE
FOLLOWING PYROLYSIS UNDER N2 AT 550°C
Polymer
Neoprene
Polyvinyl chloride
Chlorosulfonated polyethylene
Butyl rubber
Weight,
Matrecon
13.9%
4.9
0.5
%
Wakea
13.9%
5.9
0.10
asource: Wake, 1969, p. 141.
256
*U.S. Government Printing Office: 1985 559-111/10864
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