Effects of Organic Solvents or, the
Permeability of City Soils
Texas Agricultural Experiment Station
College Station
Prepared for
Municipal Environmental Research Lab.
Cincinnati, Ofl
He:!' 33
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EPA-600/2-83-016
March 1983
EFFECTS OF ORGANIC SOLVENTS ON THE PERMEABILITY
OF CLAY SOILS
K. W. Brown ai.H D. C. Anderson
Texas ASM University
Texas Agricultural Experiment St.-jtioi;
College Station, Texas
Grant No: R 806825010
Project Officer
Robert IJ. Landreth
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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TECHNICAL REPORT DATA
fF!ea c , cJ1 rn.ic::c’ j ,. e reier e e;oet ompierir.v
TREPORT NO. 2. . C Pi€ T S CC SS N NO
EPA-600/2-83-016 I PRS 3 1 799 7 R
4. TiTLE ANO SL,OTITLE
S. N PORT QA (E
EFFECTS OF ORGANIC SOLVENTS ON TEE PERMEABILITY OF
CLAY SOILS
March 1983
.PERF RM NGORGANIZATIONCOOE —
7. AUTHOR(S 18. PERFORMING IJRGANIZATION REPQRT!.O.
K. W. Brown and 1 . C. Anderson
—
9. PERFORMING ORGANIZATION NAME ANP AOC ESS
110. PROC .F .AM
Department of Soil and Crop Sciences
Tcxas A & N University
College Station, Texas 77643
R806825
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE QF REPORT AND PERIOD CO RLD
Municipal Environmental Reseorch Laboratory——Cm., Oil
Oflice of Research and De’ielopraent
Final 8/79 — 6/81
AGENCY CODE
U. S. Environmental. Protection Agency
Cincinnati, Ohio 45268
EPA/600/I4
IS. SUPPL UEr ARY NOTES
Proj ct Officer: Robert E. Landroth 5l3/ó84—7 71
1 . ABS’ AC
Traditiona1l’ , water has been usea as the fluid with which to measure
permeability of compacted clay soils to assess their suitability for lininQ
ha rdo”s waste landfill arid surface impoundments. To determine if permeability
f iner is suffic ently characteriz ;j by its being tested with water alone,
porrn abiIity studies were conducted usir. both water and a s ectrum of organic
fl s coniiionly placed in hazardous waste disposal facilities. Four clay soils,
includ rq kaclinitic, illitic, and smectitic ciay soils, were evaiuated.with the
tracitional permeability test using water, and all four were found to cualify
for lining hazardous waste dispos l facilities on t ’e basis of their havinq
perneabilitiec lower than 1 x lO cm sec . However, these same iay soils
underwent large permeabi ity increases when permeated with basic r utrai polar,
and neutral nonpolar organic fluids, and showed potential for sub tantiaI
permeability increases when exposed to concentrated organic acids. esu1ts of
this study indicate a need to test the permeability of clay liners with tever
organic fuids the liner may be exposed.
I
7. KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS b.IOENTWIERSIOPE ENDED TERMS
C- COSATI FieI iGroup
IS. DISTRISUTIQN STATEMENT I S. EC,jRITV CL.0 5 iTh zRco’ ’ , 21 NO. O AC S
UNCLASSIFIED — 16
20. SEC JRIT ’ CLASS T ’;s 9gY1 22. PRICE
RELEI&SE TOPUBLrC . UNCLASSIFIED
LPA 2flC—I ( 1t4v. 4..771 D* VIQIJl EDITION II O SO .CvL
• 1
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D I S LAIMER
Th infoni tion n this doct’ment has been fundcd ho11v or in part BY tho
United States Environrnenta Prot tion Agency wid . r Grant No. R $O6 2 O1O to
Texas A&M University. It has hee. suB ect to the Agency’s peer an’. idninis
trative review, and it has been anpro’- for p h1ication as an EPI docui nt.
Mention ot trac!e naTres or corsnercial products does not constitute endorsement
or recotnmend.3ti’n r use.
ii
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FORE W .J RD
The LS. Environmental Protection Mency created because cf
increasing public and govertiaent concern about the dangers of ol1ution to
the he ith and veif re of the American people. l oxious air, foul s er,
and spoiled land are a 1c testimonies to the det.:rioratton of our natiral
e’nvironmer’t. The comple 1ty of that environmei t and the Interplay of i a
components require a concentrated and integrated attack on the prubie;.z.
esearch and development is that necessary first step in problem soln-
tion; it involves detining the probe , measurIng its f pact, and scarc 1ng
for solutions. The iunicipal Envkronaentai Research Laboratory develops
ne and improved technolo zy and systems to prnven , treat, and masac e
ia tewater and solid and hazardous ‘astn pollutant discharges from
municipal and community s’urces, to preserve and treat public dr1nk i’g
water supplies, and to minimize the adverse economic, social, health, and
aesthetic effects of pollution. This publication is OLO of the products :f
that research ani provides a most vital communications link betveen the
researcher and the .ser community.
Francis T. Mayo, Director
Hunicipal Environmental Research
Laboratory
Iii
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A1 STRAcT
Traditional l v, w. , er has been used as the fluid it.!i which to neasure
per e bility or coniacted clay soils to assess tietr suitability for linir g
hazardous waste landtllls and surtace iopoundmet’ts. To determine if peru.e—
ability of th liner Is sufftcIent’ v characte:tz.ed by its being tested with
water i1one, permeability studies were conducted usIn both wdtor and a
spectrum of organic fluids coinnnilv placed in hazardous waste di sp siil
fae.ilittes . pour clay soils, including kaolinttic, illitic and smectltic
clay soils, were evaluated itb tLe trsditi’ina perneability test using
water, and all tour were found r quality tor lining hazardous u,te
dispos ’A facilities on the basis of theLr having perneabUlties lower th
I x i0’ cm sec . Unwever. tbes same clay soiI nJerwent large permea-
bility increases when permeated with basic, neutral polar, and neutral non-
polar otganic fluids, and showed potential (or substantial per eabiI1.ty
increases when exposed t concentrated organL: acids.
This report wag gutun I tted in full [ liment of C ntraci N . t’ b32S )1 , by
Texas A t University ua ct the spon rs tp ot the U.S. Envtton ntat
Pretert ton gencV. This report cover the period beginuirg August 197% aid
cndin June 1981, whea work was coopicted.
iv
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CO S
e 3rc I
Abbtra t
Figur# s vii
Tablea
1. Itroduct o,
. . Conciu icns.
Ste —rtie—Art Revtew
7ardous .aste Land Disposal Ov rvi n., • S
Physical Cl.ass’ s u: idaz rdou Wict
Lc1 ate Genet-ated by H zardo s .acte •
FluIcs in } azardoi Waite Lea h ite • 1)
!)rg jc Acids • ii
Orgsrtic I ascs • 13
.oitral I clar Qr anjcs 14
Noutril Nonpolar Organit • 15
Cwip nents of CLay Soils • I
‘ re p• ’i • 17
-;c, lid (;‘r po:wnt • I
:)rive or:.’anic r atter • 21
t l:i tn a1s • 22
E chan, ahle cat 1on •
Failure echanis:ms of Clay Liners . 30
Dissolution nd Pj jnc
Volune Chanpts 3 ,
Shrtuk— . 1l behavior 3
lnt rlaver spacing changes 39
Perm’ ability Measurer ent of Clay Soils 48
Materials and 1ethods 52
Fluids Studied 52
Clay Soils Studied 54
Permeability Test Considerations, Calculations,
and Prc cedut-es . . . . . €8
5 . Results and iscussion 73
73
Organic A-id Ac Ltic Acid
Orga; ic B: se — Lntjjr9 79
Neutral Polar Organi . 82
Ethylene Glycol
Acetone 82
I
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References •
Appendices
A.
I L
Mo sture—Density—PeroeabiIi ty e1at!oI s Oat a
physical U .ita on t ie Soil Co1unt Used in
the Study
C. Perme hility d ’.ta on the Soil CoIun s Used
in the Study
etl13fl )1
Neutr al onpolar 3rgir tc-s
Xylene
90
Reicitroducti n of Water
I e of Elevated } ydraui c Gradients 93
107
Ill
115
vi
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F1CU Tt’ S
Number
I Sources of Leachate Generated by Hazardous W es That May
Come contact ttlt Clay Liners
2 Cowpns!:ion of the Leachate Ceverated by Hazardous Waste . . . . 9
I Primary Leachat Ger.erated .t Hazardous waste fllsposal
Sit s - 10
4 Secondary Leachate Generated at Ilazardoas Wa ’e Dtspo a1
Sites 10
Classification of the Fluid Phases of the Leacuatrs (;ener ted
by Hazardous Waste
6 Contact Ar. le (tj) erween the Fluids and the Clay Surface. . . . 17
ffec of the Composition of ition on the Perut’abllity
of Clays 29
8 Effects of Conpaction Pator Content on th Structural
Arrar.. e ent of Clay Minerals 3’
9 Change in . Pore DIameter (400Zj Corresponding to a
Permeability Increase of 25,600Z 62
10 Forces Between Clay Surfaces as Affected b Salt
Concentration and Dielectric Constant 44
11 Compaction Moisture Content—Density Relaticnship for the
Noncalcareous Smectttic Clay Soil 60
12 Comoaction Moisture Content—Per eabil1tv Relationship
for the t oncalcareous Saectttic Clay Soil
13 Compaction Moistnr Conter.t—Density Relationship for the
Calcareouc Sractitic Clay Soil 62
16 Compaction Moisture Content—Permeability Relationship
for the Calcareous Smectitic Clay Soil
vii
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N iznner
15 Ce paction Moisture Content—D€nsity Re1ation hip for the
Mixed Cation Kaolinitic Clay Soil.
lb Corpaction Moisture Content—E’err abi1ity R. lat1onship or
the :ltxed Cation Kao1 nit1c Clay Soi 1
17 Co tp3ction M i ture Content—Density Relationship for the
ixed Cation l1l tic Clay Soil
18 Cnpaction ‘ ointure Conteot—}’er 2eabi1 ty } 1atioimhi7
tor the MIx -d Cation lIlit [ c Cia: Soil 67
19 S.’hematie of the Compact ion 1’ei ea etet
20 S hemstic of the Compaction Pernea eter Te t Apparatus
21 Porrn ability of the Four Clay Soils to Water (0.01 Ca O 4 ) . . . 74
22 Sirface of the Noncxtlcareous mectttic Clay Soil After
Passage of Tvo I’ore Volumes of Water (0.UIN CaSO 4 )
23 p rmeabi1ity of the Four Clay So1 a to Acetic Acid
2 P r eabt1ity and ‘ re kthrc . h Curves of the Four C1 v
Sotl Tr. a ed with ,e i1i e
25 Sirface (Unper left), Removed Soil (Upper right), and
the Soil a>. osed After Core Excavation (Lwer two) of t e
,%r jjnc—Treate j Noncalcarcois Sn ctitic Clay Soli 81
26 re - eability of the Four Clay Soils to F:thylene Clycol 83
77 Permeability of he Four Clay &oils to Acetone •
P(rtzeahility of the onr Clay Soils to Me Jianol and the
Breakthrough Curve for the Metha.olTr atCd Xixed Cation
‘ [ Ilitic Clay Soil $6
29 PermeabilIty of the )ethanolTrejted Mixed Cation illitic
Clay Soil at Two 1 drouiic Gradients 87
30 Surface of the Methan il—Treatcd oncalcarcor s Smectitic
ClaySoil
‘I i’crmeability and flreakthrough Curves of the Four Clay Soils
Treated with Xylene 89
viii
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be r
.12 P rr w ib 1 It, a d reakr hroUe’h Curves of the Four
Chiy Soils Treated with 11e tane.
3 Pet eabi1ity .inj reakthreu l Cu;ve for the Sor ctlcareous
S ctitic Clay 3otl rreat d e uet tl i1lv with water
(u.ulN C SO 4 ) • A jli e ar d 1 ater (U.)IN ‘
fx
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TAStES
u iw r
I l’t rc nt g of Industrial veriu un1cipal Indfill3
Rcporttd in the St i e of .vor . ta and htr. ton .. 6
2 T’ pic sl Det rtpt(nn% ot e Cor ttnt of flrw Vlaced i
j .ThaMLriJIl Lan.u ills • 6
3 1’hy ical Ci. ss4 of is ardou13 a ites • 7
4 Typical Pro ert es ot the 2:1 and 1:1 Lattice Clay Minerals. . . 23
S S ii l’o cnt1a: sus Atterberg L1 it a ues In Three
Cl: v “oils 39
6 .•rl y# r ‘ pacin s of Clay Minerals with at..r as the ,dsorbed
Eluid Ph. s’! 41
7 Tnterl tvir p:t ln o’ ( ,i1cioi ‘.rt’ct I te .as a Ft’r.et t n of
1)1.’ i •‘ t r i c (‘oi. t .in t nd Ui 2010 9c ent
P1 tr.t* rIav,:r Sp ci w ot Calcior, S’ectite I ersed in ‘hi’Is of
V ar, : 1)i” ectric Ctrnsants 45
9 Chan s f Interlayer Spacing in S ecti: tth a logoii
S-ries of ornal Monohydric Alcohols 46
10 Interlayer Spacings for Otganic Fluids t Different (pretreat—
m* nt) t hydr ttnn Temperatures 46
I1 Organic FluIds and Jater: Relevant Fhysical nnd Cta cal
l’ropert les
12 Genera] I rop rt1es of the Four Clay Soils 56
13 GraIn S1 e Di trthuti ’n of the Four Clay Soils at d Mineralogy
of the Clay S zed Fractions 57
14 Physical Poperties of the Four Clay Soils 58
IS Che ical Properties of the Fo . r Clay Soils 59
-------
Number
16 Permeability of Four Clay Soils to Water (O.OIN CaSO 4 ) . Th
17 Permeability of Noncalcareous Smectitic Clay Soil to the
Folioc ing Fluid Sequence: Water (O.O1N CaSO 4 )—Test
Fluid—Water (O.O1N CaSO 4 ) 93
xi
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SECTION 1
INTRODUCTION
Knowledge of the permeability——a main criterion used to judge whether a
compacted soil liner :ill prevent movement of leachates below or adjacent to a
disposal facility——is needed to determine a liner’s suitability for use as a
containment system. owever, little information is available concerning the
impact of waste fluids on the permeability of clay liners. Also, no simple
petineability test method has been developed that is suitable for use with a
range of possible waste fluids. Because a study evai ating the permeability
of a range of typical clay soils with a spectrum of potential waste fluids
would generate a valuable data base, the following objectives were undertaken:
1. To review briefly the testing and use of clay liners for hazardous waste
landfills and surface impoundments.
2. To delineate from available informadon the physical. classes of
fluid—bearing hazardous waste, the icachates they ge ’ erate, and the
predominant fluids in these leachates.
. To sumT.arize the available information on the components of native soils
used in constructing compacted clay liners.
4. To evaluate the potential interactions between waste fluids and compacted
clay søIl liners that may alter the permeability of the liner.
5. To develop a simple, inexpensive, and rapid method suitable for use with a
wide range of possible waste fluids, for comparative permeability testing
of compacted clay soils.
6. To evaluate the permeability of a range of typical clay soils to a
spectrum tf potential waste fluids.
1
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SECTION 2
CONCLUS IONS
A delineation of th nhysical classes of hazardous waste indicated
that many contain rganic fluids. Furthermore, the organic fluids in these
wastes may, in the presence of overburden or hydraulic pressure gradients,
permeate the liner of a disposal facility. Leachates generated by the
organic fluids in hazardous wastes were found to fall into four major cate-
gories: acidic, basic, neutral polar, and neutral nonpola: organic fluids.
Permeability reitains the primary criterion for evaluating the suita-
bility of clay licers for the lining of hazardous waste disposal facili-
ties. Permeability of clay liners has in the pas’: been determined by using
a standard aqueous leachate such as O.OIN CaSO 4 . Since clay liners nay be
exposed to organic fluids, a testing procedure was developed to compar the
effects of a standard leachate nud organic fluids on the permeahiiit of
clay liners.
Evaluation of the clay soils used to construct liners showed that t e
predominant clay minerals in these soils are smectite (montuorillonice),
iIlite, and kaolinite. Four native clay soils that contain these clay
minerals were selected for evalui.tlon of the comparative pernieab ility
proced:’res.
When clay soils used in this study are evaluated only by the tradi-
tional permeability test using water (O.O1N CaSO 4 ), all four would qualify
for lining hazardous waste disposal facilities on the basis of their h wing
permeabilities lower than 1 x i ’ cm sec 1 . But these same clay soils
underwent large permeability increases when permeated by basic, neutral
polar, and neutral nonpolar organic fluids, and they shoued the potential
for substantial permeability increases when exposed to con’entrated organic
acids.
RELATIVE PERFORNANCE OF ThE FOUR CLAY SOILS
Of the four clay soils studied, the noncalcareo, s smectitic clay soil
showed the lowest Initial permeability b it the least resistance to
increases i i permeability when exposed to organic fluids. Ti calcarcous
smectitic clay soil had intermediate initial perneability, but it showed a
much larger resistance to permeability changes than its noncalcareous
counterpart. The result was that the noncalcaree s clay generally had a
higher final permeability than the calcareous smectitic clay soil. In
2
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addition, of the t :o smectitic clay soils, the noacalcarecus tended to
yield organic fluids 3 n the effluent after less fluid had passed through
the soil.
Though the kaoliniti: clay soi. had the highest initial permeability
of the four soils studied, it nearly always showed the greatest resistance
to permeability changes. Organic fluids generaUy appeared in the effluent
of this soil after passage of greeter fluid volumes than with the illitic
or noncalcareous smectitic clay soils.
The illitic clay soil had both intermediate initial permeability and
resistance to permeability changes. But the organic fluids tended to
appear in .he effluent of the illitic clay soil after passage of less fluid
than with the other clay soils.
Overall, the kaolinitic and calcareous smectitic clay soils performed
best of the four clays studied. These two clays showed greater resistance
to permeability Increases, and organic fluids appeared in their etf.’uent
after passage of more fluid (larger pore volume values) than the illitic or
noncalcareous soectitic clay soils. Note, however, that all four clay
soils showed perweabilities greater than 1 x :m sec’ when exposed :0
several of the organic fluids tested.
RELAIIVE EFFECTS OF ORGANIC FLUIbS N ERNEABILITY OF CLAY SOILS
Organic acids appa :ently affect permeability by different mechanisms
than other organic fluids studied. The operative me hanism for permeabil-
ity changes with acetic acid appeared to t dissolution c f il particles
followed by piping of the particle fragments through thc soil. A sharp
initial permeability decrease resulted a the migraring particle fragments
clogged the fluid corducting pores. However, permea.’ility increised gt. d—
ually (with two of the soils) as the acid dissolved suil parti les that
clogged the pores.
Nc dissolution or piping was observed for the soils permeated by the
weak organic base (aniline) or the neutral organic fluids. These fluids
tended to causa permeability increases by means of eltering the structural
fabric of the soil,
Neutral nonpolar fluids caused initial permeability increases of
approximately two orders of magnitude. The soils so treated tended, low—
ever, to reach relatively constant permeability at that poInt. The basic
and neutral polar fluids showed continuous permeability increases with no
apparent tendency to reach maximum values. Though the large viscosity f
ethylene glycol and aniline slowed the rate at whIch these fluids increased
permeability relative to less viscous acetone and methanol, ali. four fluids
i. creased permeability of soils as compared to values obtained with water
(O.O1N caso 4 ).
3
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A potential exists for the data reported here to be taken Out of its
laboratory context and related back to the field. The data pre ented here
should not be used as a definitive data base for time—to—failure analysis of
clay liners. It should be noted that in the lite:ature search performed no
data were found on field verification tests of the impact of organic fluids on
the permeability of clay liners. All clay liner qualification tests
identified in the literature hive been laboratory scale usiI g various
perineameter designs.
Because of the above related effects, the results of this study indicate
the need for testing the permeability of clay liners with the organic fluids
to which the liner may be exposed. Permeability tests u ing the actual fluids
present in a waste would be an environmentally sound alternative to tests
using water only.
4
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SECTION 3
STATE —OF—TtE—ART-REV I EW
HAZARDOUS WASTE LAND DISPOSAL OVERVIEW
HCRA regulations concerning hazardous waste disposal facilities (effctive
November 19, 1981) prohibit the landfill disposal of drums containing free
liquids (EPA, 1980a). Furthermore, the regulations prohibit the disposEl of
bulk liquids in hazardous waste landfills unless the landfill has an ‘adequate
liner” and a “leachate co11 ction and removal system” (EPA, 1980b). orrison
(1981) indicated state hazardous waste regulations have done little to stem the
disposal of organic liquids in landfills and surface impoundments.
According to a nationwide industry—sponsored survey of land disposal
practices, the United States has a total of 12,62? active landfills. Of these
landfills, 40 were reported to operate wi .h lin rc ‘nd only 26 were listed as
having an operational leachate treatment and control process (National Solid
Waste lianagernent Association, 1981). The majority of active landfills are
municipal in nature and usually do not accept industrial waste (Table 1). Ia
addition, the survey of land disposal practices identified 1e9,839 active
industrial waste surface impoundments of which 69,490 are on—site facilities.
No information was reported on the number of these surface iTr.poundments that
have liners o active leachate control.
Approximately 15% of all industrial was e (57 million metric tons, wet
weight, per year) is classified as hazardo’ s Hanrahan, 1979; EPA, l9SOc).
EPA—sponsored industrial studies conducted from 1975 through 9/8 indicated that
78% of all hazardous waste in the United States is disposed of in un1in d
landfills or surface impoundments, whereas only 2% is disposed of in “tecure
landfills” (EPA, 1980c).
Cheremisonoff et al. (1979) esti .tated that 90% by weight of induatrial
hazardous wastes are produced as li’,uids. These liquids are further estimated
to contain solutes in the ratio of 40% inorcanic to 60% organic. The
heterogeneous nature of hazardous waste greatly complicates attempts to predict
its possible effect on such parameters as permeability of clay liners. However,
much can be gleaned from extensive lists of typical descriptior.s given for the
content of drums placed in industrial landfills (Table 2).
5
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T Li LE I • PERCENTAGES OF INDUSTRIA! VERSUS MUNiCIPAL LANDFILLS
REPORTED IN T E STATES OF CE0RC A tJ.L WASIIINGTON*
State
Industrial_Landfills
Muflicipal
LandfilL;
No. in State S of Total
No. in State
of
Tctal
Georgia
125 24
392
76
Washington
100 44
126
56
* National
Solid
Waste Management Association,
1981.
TABLE
2. TYPICAL DESCRIPTIONS OF THE CONTENTS OF DRUMS
I’LA.ED i INDUSTRIAL LANDFJLLS*
Dibrc.ao propanol
Methylene chlorLtu bottoms
Fractional boitams
Pesticides
Distillation b ttons
PCB waste
011 sludge
Solvent bottoms
Chlorinated still bottoms
Trichior bottoms
Ink sludge
Phenol sludge
Paint sludge
Tank sludge
Still residues
Organic residues
Terephthalate sludge
PCB bottoms
Laboratory chemicals
Sulfonated still bottoms
Reavy metal sludge
Chlorinated solvent sludge
Mercury filter press sludge
Tank bottom residues
Still bottom residues
Chlorinated organic residues
Plating sludge
Urethane laccuer
Toluene still bottoms
Methanol slurry
Resinous sludge
Phenol tar sludge
Fuel oil sludge
No. 6 fuel oil sludge
Contaminated fuel oil
Glycol waste
Heat transfer oil sludge
Acetic acid sludge
MEK distilation ottc s
Liquid resins
Freon bottoms
Oil and grease sludge
Misc?llaneous liquid a ;tes
Chlorinated xylene sludge
Benzyi alcohol bit tons
Grinding oil sludge
Filter sludge
Transformer oil sludge
Methyl chloroform bott ms
Organic siudg s
Percnlor bottoms
Waste solvents
Resins and solvents
hixed solvents
* Source: Public Records of the St .te of New York on Chem—crol Pollution
Services Scientific Landfill No. 3 containing apprc.ximately 680,000 ft 3
of industrial waste.
-------
PHYSICAL CLASSES OF HAZARDOUS WASTE
Land disposal of hazardous wastc-s an be categorized into the fol lowing
feur p “ ical classes aqueous—icorg nic, aqueous—organic, orranic, and
sludges. lois cate rization was usec., for example, in a report to Congress
(EPA, l’)74) (Table 3).
Aqueous—inorganic is the class of wastes in which water is the solvent
(dominant fluid), and solutes are mostly inorganic. Examples of these
solutes are inorganic salts, metals dissolved in inorgan .c acids, and basic
materials such as caustic soda. Examples of wastes in this category are
brines, electroplating w-istes, metal etching wastes, and caustic rinse
solutions.
Aqueous—organic is the clasa of wastes in which water is solvent and
solutes are predominantly organic. These solutes are polar or charged
organic chemicals, as irferred by their water solubilities. Examples of
this class of waste are wood preserving wastes, water—based dye wastes,
pesticide container rinse water, and ethylene glycol production wastes.
Organic is that class of w sces in which an organic fluid is solvent
and the solutes are other organic chemicals dissolved in the organic
solvent. Examples of thLs class of wastes are oil—based paint waste,
pesticide manufacturing wastes, spent motor oil, spent :leaning solvents,
and solvent refining and reprocessing wastes.
Sludges represent the fourth class of wastes. ‘They ire generated :ben
a waste stream is dewatered, filtered, or treated tor solvent recovery.
Sludges are characterized by high solids content such as found in settled
matter or filter cakes anu consists largely of clay minerals, silt, precip-
itates, fine solids, and high molecular weight hydrocarbons. Examples of
this waste are API separator sludge, storage tank bottoms, treatment plant
sludge, or filterable solids from any production or pollution control
process.
TABLE 3. PHYSICAL CLASSES OF HAZARDOUS WASTES
Waste Class
Solvent
Phase
Solute Phase
Lquaous—inorganic
Water
Inc rganic
Aqueous—organic
Water
Organic
Organic
Organic
fluid
Organic
Sludges
Organic
water
fluid or
Organic and
inorganic
7
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Both economIc and polIuLi:. contrul pressures continue to mandate
solvent recovery and reductions in discharges of fluid wastes. These
factors have and will continue to make sludges the fastest growin ; class of
wastes. After placement of sludges in a waste disposal facility, leachaces
migrate out of the sludge due to gravitational ferces, overburden pres-
sures, and hydraulic gradients. These leach tes are similar in physical
form to the first three classes of waste shown in ?able 3.
LEACHATE GE ;ERATED BY HAZARDOUS WASTE
To determine the effect of a specific waste on permeability of a
specific clay liner, two unique leachates must he Investigated. These
leachates include both the flowable constituents of the waste nd flowables
generated from percolating water leaching through the waste (F .g. 1).
Flowable constitu?nts of a waste, hereatter referred to as the
primary leachate, includes beth fluids in the waste, i.e., the ;olvcnt,
plus all components dissolved in the solvent, i.e., the solutes. Depending
on the physical class of a saste, its primary leachate may be aqueous—
organic, aqueous—inorganic, or organL. Leahate generated from water
percolating through a Jts saI facility is composed of water, the solvent,
and all components di solved or carried with it, the solutes. This
——
HYDRAU’.IC AND INFILTRATION OF
BEARING PPESSi!RE [ IDE WATER
I
!
FLUiD PORTiON
OF THE WASTE
—
PRIMARY
LEACHATE
Hazardous
[ TER SOLUBLE PORTION
OF THE WASTE
L
‘ -_____ —
I SECONDARY
I LEACBA7E
I_______
f
i
—- Clay
Liner
,
Underlying
Strata
‘ -
PlC. 1. Sources of Leachate Ceneratc by Hazardous 4astes that Nay
Come n Contact with Clay Liners
8
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flo :abLe mixture, hereafter referred o as secondary leachate, ay be
aquaJus—organic or aque us—inorganic, deper ding on waste coaposition.
The predominant flj d or sotvent phase of leachates may be water or an
organic fluid (Fig. 2). Corresponding solutes in leachates are chemicals
chat dissolve in the solvent phase. As in th physical classes of wastes,
both primary and secondary leachates are divided into a solvent phase, the
predominant fluid compc ent, and a solute phase, components dissolved in
the solvent (Fig. 3 and 4). WhIle solutes in leachates may a tect per ea—
bility of a clay liner, ths solvent phase will usually exert a dominating
influence on permeability.
Essentially all available literature describ ng leachates Renerated by
hazardous waste disposal only considers water as the solvent (t cDougall Ct
al., 1979; Chian and De alle, 197?). Water is viewed as a carrier fluid
aod organic chemicals are considered to be present in orly trace quanti-
ties. While this may be the case at the Interface of secondary leachate
and a water table, the fluli ph;se at the int rface of primary le cbate and
a clay liner will depend or, the physical class of the waste being Jis—
posed. An ornanic wast or si dge with an organic fluid phase will most
probably expose the clay liner to the organic fluids contained in the
waste. As can he seer. from Table 2, the organic fluids disposed i: a
typical hazardous waste landfill cover the spectrum of chemica. pecis.
The scheme presented above for the classification of leachates ‘.-as
previously discussed by Anderson (1981). Whii this scheme divides leach—
ates Into fluid and dissolved phases, there may also be a suspended ph s .
An example of such a sus9ended phase would be represented by the Inorganic
pigments suspended in an organic fluid saturated with paint.
FIG. 2. Composition of the Leachare Cer.erated by Hazardous waste
9
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FLUID
PHAS 1
T. 1
AQUEOUS J
FIG. 4 Secoudary Leachate Generated at Hazardous Waste Disposal
Sites
FL JIDS IN HAZARDOUS WASTE LEACiLATE
For the purpose of experimentally valuating effects organic fluids may
havt on permeability of clay soils, the fluids have been classified into four
groups. These grc•ups are based on the ‘diys cal and chemical properties that
govern their interactions with clay min3r ls. These prop rtics include
acidity, basicity, and polarity (Fig. 5). As Ci y liners are initially wetted
with water, the interaction if organic fluids with clay minerals are viowed
in the context of fully hydrated clay minerals.
Regardless of type of org-anic fluid, if it has low viscosity, it may
be leachable. Fluids with low viscosity ar Thy their very nature” leach-
able and able to extra t organic components from other wise dry waste
(Woistenholme, 1977). However, sevral other fluid properties affect
FIG. 3. Primary Leachate Generated at Hazardous Waste Disposal Sites
1 C
-------
NEUTRAL
POL&R
FIG. S. •lassif cation of the Fluid Ph&sce of the Leachates Generated
y HazarJous Waste
resultant soil permeability. Sorne of these roperties are dl cus d tth
respect to the four groups of -)rg nic fluids and water in folJ ing
sect iot’s.
anic Acids
Organic acids are or .inic fluids with acidt f tional gro* s
such as phenols and carbo ’,lic acids. Proton donating properties of
Bronsted acids g’ve these fluids potential to react tth and dls3oive
cloy soil components.
Dissolution of clay minerals in aqueous solutions of organic acids
takes place by three mechanisns as follows (Yariv and Cross, 1979):
1. Through c tion exchange, a proton repiaces an adsorbed cation
from the clay surface as follows:
Na Clay + 11011 ay + NaOH
2. Hydrogen atoms adsorbed to clay catalyze depolymerizac on of l:he
tetrahedral and ectahedral layers;
3. Hydrogen atonis diffusing Into the lattlec structure replace the
structural Al, Mg, nd/or Si atoms. These reactions are coTicen—
traced at defects tn the lattice structure or at ucleo nilic
sites of isomorphous substitution.
FLUID PHASE
11
-------
Rates of clay di ,,nlutjon i’ t ‘.a ‘tth acid concentrat. tort,
clay sr r1aee area, and MoO content of clay 1 ter1 r. D ssolnt i on aJt;o
increases with decreasing particle size, oroport lonal ro the ire r .’ t f
t me nd 1 nearLy related to the e tent, of octanedral uhst Itutiori (Sham—
berg et al., 197w).
Kaolinite, illito, and smectite are 3narin l >h . c in
d ioni ed or dt tilled water (Rat—On and Sa1 rg, 1970; and
e11er , 197i> l ut are considerably r oro olub1 n i lttt€ solut ans f
organic acds irtilar t cooponents of hu .ic acids Uiuang anc Keller,
1971). ari.v and Cross (1979) iier:tL’ led ±our avs such organic acids
could affect soluhility of clay minerals, as folloec:
I. Carhoxylic aLids replace weaker silicic ac1d that fora the
tetrtvd:al layer in clay niirai .
2. Strongly chelating acids such as several ot the dtcnrbosyitc and
hydroxy actos form stable, .oluhle, md negatively charged
coordInation complexes with Al. Fe, and g wb ch would increase
the solubility of thEse clay lattice structural components.
3. Acidic organic reducing agents convert metalli’: ox de int. their
more soluble hydroxide forms (i.e., terric oxide -. terror ’s
hydroxide).
A. Acidic organic compounds et as clay flocculating agents hich
would reduce the effect lye uri ace area of tr,e c iy mineral and
thereby reduce Its solubllit .v.
Pask and Unvis (i9 5) boiled sev.:ral clay mInerals in acid (2J h . ,O
S ) 4 ) and found the percent soluhilizat ion of alumina ra3 from knolinite,
ll Iron tIlite, and 33 to 87h from soectite. Grim (1 m ) found that 501w
biliry of clays In acId varies with the nature of the acid, the acid
concentration, the acid—to—clay ratio, and the temperature and the d irat on
of treat ’nert.’ He als found that the action of ctd on cloy was onha.cetl
when the acid had ar. calon about the same size and geometry ms a cla
component. ThIs would permit evei weak acids to dissolve clays under some
co-,dition .
Hurst (1970) found that permeability oi geologic for at1ons could be
increased by pumping in acetic or formic acid. Johansen et a!. (19 ’1)
reported flow increases for water wells following treatment with a citric
acid solution. Crubbs et al. (1972) found acid waote as probable causal
agent in permeability increase of carbonate—containing minerals. X—ray
diffraction studies of four clay minerals injected w th acid waste showed
thea to be either dtsso”ved or completely altered. [ )Lffraction peaks
showed most variability with smectitic clays.
Organic acIds in a deep—well injected waste were the major factor
involvcd in dissolution of smectitic, illitic, and kaolinttic clay minerals
(Malcolm er al., 1975). The kinetics and mechanisms for dissolution of
1.
-------
s ectit s by a variety of acids have been described by various authors
( ovak and Cicel, 19i ; Car or 4 t ai., i9i ).
An ever present source of organic acids In waste inpoundn nts is
anaerobic decn positfcn hypro:uctn. These include acotic, propionie,
butvric, isohotyric, a: d lact . acids. Peiaorobic d cc position .y e1ds
carboxvlic acid cerivatives of whatever or , anic fluids are cod In the
inpounumeat.
ALidizatton ia the mare useO for the process of increasing the perme-
ability of a porous mediuia by acid mineral dis ulution. Ths process Is
widely used to increa:o per ani1itv and hence productivity of oil wells
(Sinex. 1970).
i.aterial that. incrusts at the base of wells used for deep—well waste
injection usually cou ists ol c lciutn, nesiun, and iron carbonates,
nlon with lnbeddcd sand itnd clay particles. Ic remove carbonate com-
pounds, they must be dissolved and I d in solution against precipitation
forces. Dissolution is usually accorplished with a stong acid. talcium
will reprec pitate as caictuia sulfate to the presence of sulfuric acid,
UflICSS It Is chelated and romov&d by a flowing fluid. ChelatIng agents
effective at pre cntin reprectpitat ton ot various carbonates are tric
acid, tartaric acid, and glycolic acid (Anonymous, 1977).
Orranic gases
Bronsted organic bases are organic fluids capable of accepting a
proton to become au ionized cation. Since these fluids are poaitively
cha.ged, th y adsorb strongly to the negatively charged clay surtaces.
Through adsorption, tnese fluids may replace adsorbed waler which would
alter the chemtstry of the clay surface and change the behavior of he clay
soil. While it Is nut clear if organic bases are strong enough proton
acceptors to do so, inorganic bases are known to dissnive certain compo—
ruents of clay minerais.
Bases have been implicated in tht dissolution of clay liners. Haxo,
Jr. (197 ) found In preliminary tests that smectitic clay liners allow
passage of both strong acids and strong bases within a short period of
time. Nutting (1943) showed that eien extremely dilute solutions of alkali
effectiveJy removed silica from smectites by dissolution of the crystal
lattice.
Industrial sludges, such s sLill bottor s, crude tank bottoms, and API
separator sludges, contain significant amounts of corapounds with polvcvclic
condensed rtng structures. These co otmis often contain basic nitrogen
groups in their ring structures (nitrogen helerocycles). When put in
contact with clay minerals, the protona ed, positively charged nitragen
groups are elcctrostattcaliy attracted tc the negatively charged cloy
surfaces. As these baste organic comt unds approach the clay surface, two
other forces of attra ’ tion come into play. First, their large molecular
13
-------
waights would generate strong van der Waais attractive forces. Secondly,
there would be Loteractions between the pi electrons or the aromatic groups
with either the exchangeable cations or the oxygens on the surface of the
clay (Clementz, 19Th). Adsorption of these compounds by clays has been
found to be rapid and nearly irreversible while yielding a prous matrix
that is structurally stahe under either aqueous or organic fluii flow.
With adsorption of organic cations, the charge density of the clay
will affect the r snlting interlayer spacing. Weiss (1958) found the
interlayer spacing after exposure to alkylammoriium ions to be 1.3 on, 1.9
nm and 2.76 ram for smectites with low, medium, and high charge densiies,
respectively.
Ne’itral Polar Organics
Neutral polar crgar.ic fluids do not exhibit a net charge but have an
asymmetrical distribution of electron density resulting in an appreciable
dipole ‘In’aent (an india -star of polar character) (Debye, 1929). This
property a ows polar compounds to compete with watar for adsorption sites
on the acgatively charged clay surfaces. As war indicated in the case of
organic catior.s, the adsorption of an organic fluid to clay surfaces will
change the D havior of the clay soil. This altered behavior may ir clude
chai yss in permeability of the clay. Examples of such polar compounds are
alcohols, aldehydes, ketones, glycols, and alkyl halides.
Gruhbs et al. (1973) found that a neutral polar organ .c, methanol,
increased per eability of a core previously injected with oil—based
wastes. Re also noted use of solvents, organic acids, surfactants, alco—
nols, and emuision breakers for permeability enhancement in deep well
injection operations.
Brant (1968) found an increase in the permeability of a soil to water
after treatment with 4—t—butylcatechol. Re postulated that the permeabil-
ity increase was due to the soil matrix being rendered au’ re stable to water
flow. This increased soil stability caused a decrease in migration of soil
particles that would have otherwise clogged soil pores.
Neutral polar organic fluids tend to reduce surface tension exhibited
by water. The decrease in surface tension (and hence viscosity) of a fluid
would significantly increase permeability of a soil as measured with that
fluid. Letey et al. (1975) foun that permeability of a soil increased
with tine if rhare were substances in the soil that were miscible with and
decreased the nurface tension of water. Additicnaliy, Miller etal. (‘ 975)
foun’i that permeability of a soil increased as wate flushed out an earlier
application of a surfactant.
MacEwan (1944; 1946) demonstrated that a wide variety of polar organic
fluids would adsorb to the center layer surfaces of both smectites and
halloysit ’ s. Theng (1974) found that polar compounds can be adsorbed to
these aurf aces by van der bJaals forces Including hydrogen bonding and
14
-------
dipole—dipole inter ictions. Additionally, these compounds can be adsorbed
through ion—dipoie interactions with the exchangeable catlons o the clay.
Neutral Nonpolar Organics
Neutral nonpolar organic fluids have no net charge nd small if ny
dipole moments. These fluids have lOW water solubilities and ii tle polar-
ity with which to compete ith water or adsorption sites on clay miner-
als. However, in the pre etice e a hydraulic gradient, nonpolar fluids
move downward through a c ay w thout being appreciably attenuated by clay
minerals. Examples of nonpolar organic fluids are aliphatic and aromatic
hydrocarbons.
Van Schaik (1970) iound that the permeability c f three soils was
consistently higher for a neutral nonpolar oil than for water. Michacis
and Lin (1954) obtained small permeability increases in a knoliuttic clay
when a polar perneant fluid was replaced with a nonpolar flukd. They f mmd
that the permeability increase was greatest (10—30%) when the polar fluid
being replaced was water.
In a study of permeability of a clay subsoil underlying a proposed
landfill site, White (1976) found the clay soil to be highly imperneabl to
water and very pcrmeable to lighter hydracarhoes. The study concluded that
ur.der optimum corpaction, a three foot liner of the clay i t t a tank 23 feet
deep containing heuzene can begin to leak vitinit 16 days. If the clay
soil was compacted at moisture contents belo 31%. it was mc i 4 erably : cre
perceable to the neutral nonpolar fluid beazene.
A significant factor in the initial disp’acement of water from a com-
pacted clay by a neutral nonpolar organic fluid is the interfacial energy
that would exist between the two relatively immiscible fluids. Lambe and
Whitman (1979) mentioned this interfacial energy as the reason why, accord—
1mg to these authors, oil can be stored with “no leakage” in prehydrated
clay lined reservoirs. While this may b . the case for the short term
storage of a honogenous neutral nonpolar organic fluid, its validity for
the heterogeneous fluids present in hazardous waste has not been deter-
mined.
CertaIn neutral nonpolar fluids (n—paraffins) have been ahown to
adsorb to interlaver spaces in sinectites (Barrier and McLeod, 1954). The
usual mechanism for adsorption of nonpolar compounds is by physical adsorp—
tion (i.e., van dtr Waals forces) (Theng, 1974).
Water
Water is a unique fluid In several ways. It exhibits a large dipole
moment which allows it to strongly adsorb to clay surfaces. The ability 0 f
water to hydrogen—bond to itself permits it to adsorb in muitiple layers on
15
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clay and form large hydration spheces around Inorganic s .11 cations. These
?roperttes give water the ability to cause certain - lay soils to n e11 and
seal upon hydration and shrink and crack if wateris displaced or extracted
from the ciay. The role of water in volune changes of clay soils is
further discussed in a inter section. As mentioned ‘ riicr, cmv surfaces
in a clay liner are initially water—wet. It however, a percol t ng organic
fluid has a higher affinity for the clay sut acc than water, t ie clay may
become organic—wet (Raza et al., 1968).. For example, water and oil ace
said to compete with each other for solid surfaces in oil re ervoirs. A
quantitative measure of the preferential wettahility of a clay surface for
water and an organic fluid can be represented as the difference between the
water—clay and organic- clay interfacial energies b the Your.g—Dupca equa-
tior. (Adams, 1941) as follows: -
( -yorg:c) — ( -yw:c) (yorg:w) (cosO )
where:
‘y’ org:c = interfacial energy between organic and clay
(dynes/cm)
interfacial energy between water and clay
(dynes/cn)
org:w Interfacial energy between organic and watcr
(dynes!cm)
0 angle at the organic:clay:water interfac” measured
through water (degrees)
Th.fre is no direct method for measuring either organic:clay or water:
clay interfadal energies (Raza etal., 1968). Their difference, however.,
Is equivalent to the product of the water:organic interfacisi energy and
the cosine of the water:clay:organic contact angle, 0 (Fig. 6). This
coittact angle is easily calculated from capillary rise measurements of th
fluids (Baveretal., 1972).
Since the clay surface is negatively charged, polar or positively
charged organic leachate components will have an affthity for interlayer
surfaces of an expandable lattice clay. Water on the clay surface may be
several layers thick, and thus water solubility will improve access of an
encroaching fluid to the clay surface. The strength with which water binds
to a clay surface will vary with cations adsorbed and clay charge density.
However, these factors may change from one place to another in a clay
liner. Reviews of interactions between Interlayer water and clay minerals
recently have been published by Low . .1979), Low and Margheim (1979), and
Thong (1974).
16
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FIG. 6 Contact Angle (6) Between the Fiiyjds and the Clay Surface
COMPONENTS OF CLAY SOILS
Physically, a day soil is a porous mixvure of air, water, organic
matter, and inorganic minerals. Vo1umetrica ly, a clay soil ccntaths
approximately 40% pore space (occupied by a r and water) and 6G% solids.
The solids conrain trace to 157. organic mattet ard 85% to graater than 99
inorganic minera-s. In clay soils, these inorganic n neral are sand
(0.05—2.0mm) and silt—sized rock fragments (0.O2—O. )5inn) and at least 35
clay—sized par:icles (
-------
size and permeabilit\ was consistent with “tt e well—known fact that pore
size distribution rather than total pore volume governs . . . permeabil—
ity.’ Similarly, large pore formation was determined to be the cause for
permeability incr as s in porous media treated wit} acids (Schachter and
Gidley, 1969). Acid Js cotmonly injected into oil wells to increase the
permeability of ;in oil bearing armation in the region of the well bo [ e.
Structural devel .’pmnnt has long been considered to he responsible for
the presence of large pores in clay soils (Lauritzen and Stewart, 194’.). A
major force behind structural development is the shrinking and swalling
that clay soils L:ndergo with changes in water content. Consequently, if an
organic leachate displaces or extracts water from a clay soil, there ay be
an increase in both the number of macropores and thus permeability.
Pore size distributions ind total poresity of smectitic, kaoilnitic,
illitic, and halloysitic subsoils and comnercial clays were determined by
Diamond (1970) using the mercury intrusion porosimeter. This method of
evaluating pore size distribution is 3ased on the principle that non—
wetting fluids, i.e., fluids irh contact &w!cs (6) (Fig. 6) greater than
90° for the solid phase, will only enter a given size pore if sufficient
pressure is applied .‘4ashhurn, 1921). Thus, mercury Is forced under pres-
sure £nt> the dehydra ed and evacuated soil sample. Applied pressure is
increased increuentaily while the volume of mercury entering the soIl Is
recorded. A pore size c’istributin curve is obtained by plotting pore size
against cunulative pore volu:ae while using the following relations In to
convert pressure applied to pore radius (Nagpal etal., 972):
P 2 cos S/r
where:
P applied pressure
X surfaze tension of mercury
6 contact angle of mercury
r pore radius
Another method for determining the pore size distributIon of soil is
the pressure plate technique. This method Is based on the incremental
increase of sucti:,n on a soil requirr d to remove water from progressively
smaller pores. The equation used above also applies to the pressure plate
methods where the variables are suction (P), surface tension of water
-------
Either clay, when compacted on the dry side of optimum moisture*, e; hiblted
more large pores than when compacted on the wet side of optiraum moisture.
A hydraulic head (h in cm of H 2 0) has been shown to displace water in
a pore with an equivalent radius (in micrometers) of approximately O.15h
(Marshall, 1959). Where water ii being displaced by an immiscible or
non—wetting fluid, there iou1d be an additional energy barrier retarding
the dispiacenent f water equal to the interfacial energy between the two
fluid phases.
An exten;ive review of pore space in soils and mechanisi .s of pore
formation in relation to soil structure and fabric has been pubiished by
Brewer (1964’. The publication also covcrs principles of fabric analyris,
classifIcation of voids, and techniques for structural. anaiysis.
Soil fabric or structure has been defined as the physical constitution
of a soil material as expressed by the spaclal arran ,ement of the solid
particles and associated voids (Brewer, 1964). VoidS, interconnected
spaces between the solid components, are classified according to their
size, shape, arrangcment, and morphology.
One slze classificatIon scheme for soil voids includes macrcvo ds
(>75 m), ntesovoids (3 ’l_?5j m), and ultramicrovoids (<5inn). The minimum
value for macrovoi is (75 jm) was chosen to corres?ond with theoretical mini-
mum dIameter pores from which waler would be displaced under -,uc on or
hydraulic head of 41) cm of water (Brewer, 1964).
Snape classification schemes for soil voids Include those that deal
with both coarse characteristics and minute surface details. Examples of
coarse characteristics are length of the principle void axis, degree of
void curvature, and ‘:egularicy of these features. brewer (1964) described
a void classification based ott relative smoothness of void walls on a
micros cal e
Two void classes based on nicroscale surface snoothness are o thovoids
and meta oids. Orthovoids are “voids whose walls appear mor hologLcally to
be due to t ae unaltered, normal, raiidom packIng of plasma and skeleton
grains” ( r wer, 1964). “Plasma represents relatively mobile a d unstable
solid constituents of soil, while “skeleton grains” represent relatively
stable and irmobile soil matrix. Metavoids have smoother sides tlan ortho—
voids. Under pressure, slicken—sided metavoid walls show evEi ence of
diffureatial movement of parallel planar surfaces (Brewer, 1964). In
gene al, the larger the void, the smoother the void wall. Con ;et uently,
the void wails of an ultra mLcrovo d (such as those within soil aggregates)
wruld generally be c J.±ied as orthovoids. Macrovoids are generally
vjetavoids due to their relatively smooth walls.
Void arrangements refer to distribution arid orientation of individual
vc•ids. Distribution cf voids in relation to the basic soil aggregate or
*( ptimum moisture refern to the water content of a given soil for which a
given compactive effort wIll yield the maximum bulk density.
19
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ped has been divided into intrapedal (voids within peds), interpedal (voids
between peds), and t anspedai (voids that traverse the soil material
without specific associations vith indiv- dua1 peds) (Brewer, 1964).
Further distribution classification can he based on void groupings such a
randorn , handed and clustered. Orientation of the voids can be classifi d
as parallel or one of several brancMng patterns (Brewer, 19b4).
!orphologically, Brewar (1964), divided voids into packing voids,
vughs, resides, channels, ci-ambers, and planes. Packing voL4s are due to
random packing of the individual soil particles. Vughs are larger than
packing voids, irregul. r in shape, and may be interconnected. Vasicles are
different from vughs in that they are r gular and snooth—walled. Channels
are large and roughly cyltndrtcal in shape with smooth walls and a fairly
unif.rm crossectiom. Chambers are different from vughs in their smooth and
regular walls and different from vesicies and vughs due to the interconnoc—
tion of the chambers by channels. Plnes are simply planar voids that arc
further divided into j’)int planes (traverse the soil, in regular patterns
and series), skew planes (traverse soil in an Irregular manner with no
identifiable pattern), and craze planes (planar voids with a highly complex
netwoik of interconnecting short, fat, and curved planes).
Clay minerals have been implicated in at least two types of void
formation (Brewer, 1964). Otthovughs are large voids that tend to form in
soils with wide particle size distributions. Fcrnattoa of these voids
occur when conditions exist tnt flocculation of clay minerals present on
surfaces of skeletal grains. Should these orthovughs be interc ’nnectnd,
permeability of the soil would increase dramatically. Clay minerals are
also responsible for the formation of systems of cracks and planes from
shrinking and swelling that accompanies changes in water content.
As voids are easenti ti to u derstanding pore space in soils, curans
are essentIal to underst t ing voids. Cutans have been defined as a modi-
fication of the texture, 5 r ’ucture or fabric at natural surfaces in sofi
material due to coucentrat .or. of particular soil constituents or in situ
modification of the plasma; cutans can be composed of any of the co poneat
substances of the soil material (Brewer, 1964). Irt other Otda, cutans
are coatings on the soil skeleton that actually form the wall surfaces of
soil voids.
Cutans have beer, clasnif led according to the kind of surface hev
coat,the nature of the cutanic or coating materIal, and spacial arrange-
ment or fabric u thin the cutanic rw- mrial (Brewer, 1964). Cutans classi-
fied according to the surface with wiich tney are assoniated thclude graLr.
cutans (associated with skeletal grain .iurfaces), ped cutans (assoctatod
with ped or aggregate surfaces), channel cutans (associated with channei
surfaces), and plane cutans (associated with planar void r.urfaces) (Brewer,
1964).
Cutans have also been classified according to the mineralogy of the
cutanic material. Argillans (cutans composed primarily of clay minerals)
are the most significant cutan in compacted clay soils. A further subdivi—
sion of argillans can he made hosed on the following criteria: kind of
20
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clay mineral, size and shaç’e of clay rilneral particles, coating thickness,
and contaninants adsorbed to the clay minerals (Brewer, 1964). Two impor—
tact argillans subdivided according to contaminants associated with the
clay minerals arc terri—argilians (clay ninerals mixed with iron oxides or
hydroxides) and organo—argillans (clay minerals stained with organic
compounds).
Clay minerals are probably the most dynamic cutanic materials d e to
their ability to go into suspensions and readily undergo reorientations
(Brewer, l9 ’4). Strong orientation of the plasma associated with a cutan
is indicative of its being formed from migrating clay mInerals. urther—
more, the voids formed from clay iiluviation (migration) tend to he associ-
ated with water—conducting oids.
Solid Coj nents
Solid components that dominate behavior of clay soils are organic
matter, clay m erals, and cations adsorbed to clay ninetals. Organic
matter generally imparts structure to clay soil and results in larger pores
and higher permeabilIty (Brady, 1974). Low permesoility usually associated
with clay soils, however, is due largely to characteristics o: clay
minerals and associated cations.
Native Organic atter
Soil organic matter conststs of partially decomposed plant and animal
resIdues and humus. The residues consist of approximately 6O carbo mv—
drates (sugars, starches bemicellulose, and cellulose); 2S lignins
(exeeedi gly co ple’s, waxy, resinous material); S fats, waxes and tanmii s;
and IOZ protein (Brady, 1974). Gieseking (1973) edited a recent text that
ccntained chapters devoted to the following native soil organic constftu—
ents: saccharides, nitrogenous substances, organic phosphorous coirpounds,
organic sulfur compounds, fats, waxes, resins, and hunic substances. Humus
has been defined as “a complex and rather resistant mixture of brown and
dark brown amorphous and colloidal substances modified from the or 1 ginal
(plant and animal) tissues or synthesized by the various sot] organisms”
(Brady, 1974). By far the most active part of soil organic matttr, as far
as its impact on physical and chemical properties of soil, is the co]—
loidal humus fraction. !um 1s is composed c. negati elv charged colloids
with surface areas and cation exchange capacities far exceedirg even smec—
titic clays (Brady, 1974). Negative charges of humos are highly pH depead—
ent .greater CEC at higher pH). These charges arise from the carboxylic
acid and phenolic groups that are abundant on humic substan:es.
Through interactions with the clay fraction of soil, humus and other
organic constituents are largely responsible for formation and stability of
soIl aggregates. Clays have been shcwn to interact with many soil organic
21
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constituents ,och as hunus (fulvic acid, humic acid, huriin, and hynatomei—
anic acid), proteins, organo—phosphorous compounds, cellulose, he icellu—
lose, and others (Kc’nonova, 1975).
For centuries it has been understood that soil organi constituents
Impart to soil a highly aggregated, porous, and structurally stable charac-
ter. Clay soils with nornally low permeabil ties can be transforned into
highly pervious soils by the additicri of organic matter. Thus, in an
effort to simulate the acci n of humus on structure and permeability of
clay soils, several synthetic “sc.il conditioners” have been developed.
Examples of these organic onpounds are pGlyvinyl acetate, polyvinyl
alcohols polyacrylamide, polyethylene glycol copolymer, styrene—acrylic
acid ester polymers, and many others (Schamp etal., 1975).
It is interesting to note the similarity between some c amcnly
disposed industrial organic sludges and the commercially avaii’able soil
conditioners (Ta’ie 2). it h is been a common u iderstanding among f ’r-rners
the world over that adding organic constLtuents to poorly drained clay
soils can greatly anhance soil structure and drainage properties. The
Chinese 1-i v, for centuries added organic human wastes to improve tne q 0 fl
structure of f rmiand. Recently, hazardous waste land treatment facilities
have found that adding organic sludge to clay soils tends to transfrm the
clay into a highly aggrcgate and very porous bed. While organic r cterjal
imparting stricture and porosity to clay soils Is advantageous to the oper—
atior of hazardotis waste land treatment facilit! s, it may he a bad ornen
for the long term integrity o clay liners.
Hydrophobic surfaces in clay soils are usually for’ ed by certaIn frac-
tions of native organic matter coating clay surfaces (Let y etal., 1975;
Letey t al., 19f ). These “waler repellent” soils eneraily have
decreased permeability to water but ¶c’creased permeability to organic
fluids.
Clay titierals
Clay minerals are composed of repeating n ate—like structures of
Sio 2 tetrahedral and AL O 3 —octahedral lattice sheets. Two besic c hina—
tions of these lattice sheets are represented in 2 1 clays, which consist
of one octahedral sheet sa ,dwiched het’. een two tetrahedral sheets; and 1:1
clays, which consist of one octahedral and one tetrahedral sheet. Further
differentiation of clay minerals are made on the basis of the iegree to
which adjacent repeating layers are expandable or by the geoneiric shape
taken by individual clay particles. Table 4 lists the relative sizes and
values for several properties of 2:1 and 1:1 clay minerals.
In native clay soils and subsoils, the clay nineral. fractiort is usual-
ly of mixed mineralogical composition. Sever..l clay ulneral spcc!es are
normOll7 present with one or two species dominating. In the following two
sections, four of the most widespread clay ni eral species are discussed.
22
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TABLE 4. TYPIC. ’ t. PP’c 1ES OF TUE 2:1 and 1:1 LATTICE CLAY MINERALS*
MIneral Na ie
and Lat tce
Description
Unit Pa
rt.Iclc ’ ThIckness
Specific
Snare Area
(n’ / m)
Exchango
Capacity
rneq/ I 0(’grn
Unit Particle
Size
t ’ thtckrt• s
1 lem; iii
Particie
Sh apO
—
Cun ra teT
(n )
Uydr entT T
(nm) Vj1
Chmge
Smectite
( xpand ble
2:1 lattice)
2.0
6.0 20O
‘JU
100
1
—
Flaty
Illite .
on—expandao1e
2:1 lattice
20.0
22.0 10Z
E0
10—40
t - 4 L
1t
Platv
(Non—e dabln
1:1 lattIce
200.0
202.0 1%
8
3
t 1,
Pluty
Hallovstte 70 nm(outsjde
(Expandabic 40 ni (lnside
1: 1 latt ice 500 nn:( length)
diameter
diameter)
40
12
(
1
t L
who rc our sLIc
dIa; ctcr)
Hollow
tuhc
‘-I
*Fro . : Cri a (196a); Lainbe and Whitman (1979); Theu ; (1974).
-------
These are 2:1 expandable layer smectites, 2:1 non—expandable layer illites,
1:1 non—expandable layer kao1ir ites, sad multiple form 1:1 balloys .tes.
2:1 Clay Minerals
Clay minerals with 2:1 nttice c’ .iiigurations include the smectitic
and illitic clays. These clays have iJeutical structures except for the
bonding mechanisms between adjacent repeati i layers. Smectite layers are
only loosely bound resulting in a clay with large capacity for volume
changes. Illite layers are tightly bound by interlayer potassium ions
resulting in a clay with little potential for volume changes. Recent
revIews of thase clay minerals have been edited by Dixon and Weed (199).
Sinectite . Smectitic clays have a lar-ae cation exchange capacity (100
meqflOO go), speciflc surface area (800 n’ /gn), and potential for volume
change (200 ) (Tabis 4). These properties co.nblne. to give smectites the
potentially lowest and highest permeability values of clay m nera s. Low
permeability h. due to small unit pacticlc size and large capacity for
swelling with water adsorption. Smectitic clays derive high perneabilities
from their ability to shrink und crack with water loss.
Smectites have large canon exchange capacitir s due to t -cir large net
negative surface charge. The nogative charge comes fr n FeZ+ or
isoinorphous substitution for Ai 3 + in the octahedr ’l :;hc et, or A1 3 + substi—
tct1.on for si 4 in the tetrahedral sheet. Cations adsorb to interlayer
surfaces of the clay to balance the negative ha e arising f orn wit iin he
2:1 lattic structure (Grim, 1968). The isom ;phous sjbstitution discussed
above is the predominant source of charg- on smecti es, ut toere is a
small pH dependent, amphoterfc charge associated with broken r onds at edges
of the clay crystal (long and Warkentin, 1915).
Adjacent 2:1 l3yers of smectitic clays are only loosely bound by
interlayer catior.s. Sciectites readily swell in water from hydration of
Interlayer cations and adsorption of multipie water layers on iciterlayer
surfaces. Table 4 iLlustrates that when dehydrated, two smectite layers
have a thickness of 2 mm. Hydrated sniectites can, however, swell to over
200% of tnis thi kness by adsorbing four layers of water on each of the
four available interlayer surfaces.
Clay soils high in smectitic clays usually have very low permeabili—
ties when fully hydrated. However, these soils tend to develop deep and
wide cracks when dehydrated (Bayer. ! .8!., .972). AnythLng that could
cause a loss of water from a compacted smectitic clay liner could cause
shrinkage cracks to form. These crarks wouli cause permeanility )f the
clay liner to increase several orders of magnitude.
Extraction of interlayer water has been cited as the cause of shrink-
ing and. cracking in smectitic clay soils Baver, et al., 1972; Grim,
1968). Shrinkage due to renoval of interlayer water assumes a decrease in
thickness of the water tilru surrounding individual smectite particles.
2
-------
However, coil smeetites between suction values of zero to 1.36 x 10 mm Hg
are assumed to have a constant ..ater film thickness (Emerson, 1967).
Th’ refore it blould seem that bulk shrinkage of smectitie clay soils at higt .
water contents (0—2.72 x io mm Hg of suction) cannot be totally explained
by removal of interlayer water. In a study of the shrinkage characteris-
tics for 59 clay soils at high water contents, water film thinning was
discounted and deformation of pores was a aumed responsible for the shrink-
age observed (Greene—Kelly, 1974). Since clay lJ.ners are usually kept
moist (if not saturated) in the landfill environment, any significant
degree of shrinkage would probably involve a more compact repacking of soil
particles accompanied by changes in the pore size distribution.
Thickness of the water layer between adjacent sneetite lattice sheets
affects plasticity, interparticle bonding, compaction, and water movement
within clays. These properties change as thickness of interlayer .iter
changes (Yong and Warkentin, 1975). Examination ci forces holding water to
interlayer surfaces in smectites will assist in predicting the effects of
an intruding organic leachate on interlayer spacing in clay liners. It is
widely believed that water layers immediately adjacent to smectitic clay
surfaces are non—lhiuid, hexagonally structured, and held more strortgiy
tian water layers further out from the surface (Grim, 1968). Thickness of
this structured ‘ater varies depending on the adsorbed cation. Stsectites
have a structured water thickness of 1 mm or four water layers per clay
surface when calcium iS the adsorbed cation. Sodium smectite has a str’ c—
tured water thickness of 0.75 r.m or 3 water layers on i s surfaces (Grim
and Cuthbert, 1945). Glaeser (1949) found, however, that the distance
betceen dehydrated smectite l vcrs exposed to acetone increased to 1.25 no
and 1.51 nm when sodium and calcium, respectively, were the adsorbed
cartons. Thus, propertias of smectit s vary greatly depending on the
distribution of exchangeable cations (Yong and Warkenlin, 1975).
Surface—hound layers af er are held strongly to the clay. tiowevel,
they represent only part of interlayer water. Water layers further out
from clay surfaces are held i• place by hydrogen bonding, formicg chains
extending back to structured w ’ter layers a ichored to the clay surface.
These outer layers of water can more easily be displaced by an intruding
fluid. Smectitic clays have beer, shown to interact with nitriles, esters,
and ethers (Hoffman and Brindley, 1960), organic bases (Theng, et al.,
1967; Cloos et al., 1979), aromatic compounds (Greene—Kelly, 1955), alco-
hols (Annabi—Bergaya et al., 1979), surfactants (Erindley and Rustom,
1958), polyvinyl alcohol (Greealand, 1963), ketones (Parfltt and Mortlar.d,
1968), glycols and glycerols (Hoffman and Brindley, 1961), and se ral
polyfunctional organic. liquids (Zradley, 1945). Several good reviews of
these interactions nave been published (Theng, 197k; Mortland, 1970).
Sinectites readily adsorb polar and positively charged organic species
on interlayer surfeces. Since sinectitic clays can swell in water to 200Z
of their dehydrated volume, large amounts of shrinkage can occur if inter—
layer water is displaced by other fluids which yield a lower interlayer
spacing.
25
-------
Irterlaver spacing in smectitic clays increases a the dielectric
constant and dipole mo ent of the adsorbed fluid increase (Harshed, 1952;
Grim, l9( ). Sia e w cer has both a very hi ,h dielectric constant anc’
dipoie moment, tts replacement in clay interiayer spaces by most polar
organic rolvents would cause significant decreases in interlayer spacing.
interlayer shrinkage, even just along large pore wails, could cause signlf-
leant increases in perm abil1ty of a clay liner.
illite. IlUte is a field ter, loosely defined as clay sized nica
ceous minerals. These :lays have specifIc surface area (80 m 2 /gm), cation
exchange capacity (1U- () icq,’IOO gm), and potentiat for volume change (1OZ)
intermediate between smectite and keolinite. lilite also has intermediate
particle thickness relative to the other clays listed in Table . As with
smectitea, the soerce of charge in illitic clays is i onorphic substitutien
in the clay lattice and to a lesser degree the pU dspendent charges on
broken bonds at edges of th. clay crystal (Yong and Warkentin, 1975).
1iany illitic otls are actually admixtures of interstr tified struc-
tures of illite, s nectite. and vermiculite (Theng, 1979). Hence, there is
wide variation in couposi ion and physiochemit-al properties associated with
this clay mineral.
A4jacent illite layers are tightly bound by interlayer potassium
cations fixed between repeating 2:1 layers. Consequently, this non—expand-
able clay usually will not adsorb water or polar organic fluids on inter—
layer surfaces, This interlcyer exclusion causes illite to have potential
for no mre thaii IOZ shrinkage or swelling. However, Macintosh et a).
(1971) found that an organic cation that closel, approximates the size and
charge of potassium . such as dodec.vlan moniuta) could replace this cation in
the interlayer. Except in the rare case stated above, adsorption o or ’,an—
Ic chemicals will lsrgely be coefined to external unit particle surfaces.
illite—silt mixtures have been shown to undergo decreases it: perrica—
bility with decreasing electrolyte concentration : ol1owed by permeability
increascs if the electrolyte concentrations were subsequently Increased
(Hardcastle and Mitchell, 1974). The permeability increase appeared t the
authors to be due to a slight decrease in clay swelii .g.
lilitic clays have been shown to interact with organic bases (Macin-
tosh et al., 1971), organic acids and peptides (Greciland Ct al., 1965),
organic polymers (Schamp et al., 1975), glycol (Parfitt and Greenland,
1970), alcohols (Greenland, 1972), and proteins (Albert and Hatter. 1973).
Recent. reviews are available that summarize the literature dealing with
illite interactions with low molecular weight organics (Theng, 1974) and
organic polymers (Theng, 1979).
1:1 Clay Minerals
Kaolinite is both a general term for 1:1 layer clay minerals and a
specific term for 1:1 non—expandable clays. Another nember of the 1:1
clays is halloysite whLc t has h: drated interlayera and is shaped like
hollow tubes. There appears to be continuous gradations between :hese two
26
-------
1:1 clay minerals (CarroU. 1910; Ther,g, 1979). These clays obtain their
exchange capacity both iron ph dcpen ei t harges on broken bonds at edges
of the clay crystal and tonizati.n of vdroxyl groups on basal surf .ces u’
the clay (Yong and Warkentln, 19I ). A g.,netal re.’iew of these clay niner—
als has been written by Dixon (1979).
Kadloite (Species). Kaolinitic clay has low cation exchange e pacity
(3 meq/l00 gn), specffic surface area (8 m 2 !gn), and only snail potential
for volume change (Table 4). Adlacent 1:1 layers are tightly hound by a
netwrk of t ydrogen bonds that usually prevents interlayer penetration of
fluids (Grin, 1968). The 1:1 layers are stacked into hexagonal 7latelets
ranging in thickness from 0.05 to 2.0 m. Except where the interlayer
space has been e:panded by certain inorganic salts (Wada, 1961), orRanic
fluids only adsorb to external surfaces of the hexagonal platelets.
Kaolinite has been shown to Lntera.t with organic bases (Grim et al.,
19!.7), amines (Conley and Lloyd, 1971), polyvinyl alcohols (Greenland,
1972), organic acids ( ..vans acd kuss ll, 1959). polymers (Sakaguchi and
Nagase, 196(), alcohols (German and Harding, 19h9), and various other polar
organic compounds (Olejnik et al., 1970). Loeppert et al. (1979) invest!—
gated the influence of ha ic, polar, and nonpolar organic fluids on the
acidic crystallir. . edge site of kaalinite. The Influence of po’ar and
nonpolar organic fluIds on per eabti1ty of compacted kaol!nite was itwe ti—
gated by Michaels and LIn (1954). They found that changing froo water to a
nonpolar organic fluid could cause significant peraeabi’..ity increases.
I a1iov ite. Halloysitic clays are similar in cum )o5ition to kaolfnfte
with t’ie exception of interlaver bonding ?ad geosietric configuration.
Instead o hydrogen bonding between adjacent layers, belloysite often a
tubalar ?eolnetric configuration when viewed in the dehydrated state by
electron lcroscopy (Theng, 1979). ;(ydrated ai1oy lte has a larger
specific surface area 4O nh/gm) and cation exchange capacity (12 meq/gm)
then kaolinite.
Hallc jslte has been sLosa to interact with a variety of erganic
compounds (Carr and Chlh, £911) such as glycols, ethers, alcohols, amines,
ketones, aldehydes, nitriles, nitroso—compounds (MarEwar., 1948; Mac wan,
1949), and amides (Weist and Russow, 1963). While the kaolinittc spe:ies
generally do not permit int rlayer penetratIon of ater or organic
fluids, halloysitic species readily adsorb polar and basic organic fluids
or. interlayer surfaces (MacEwan, 1948).
Another noteworthy property of halloysite is its amphoteric nature.
That is, halloysite may exhIbit either positive or negative charges depend-
ing on the pH. Ore aide of h lloysite h a a network ‘f hexa or.ally
arranged oxygens, whereas the other side is a network of hydroxides (Tlaeng,
1979). Geometrically, halloysite graduates from slightly curved hexagonal
platelets (hydrated) to individual 1:1 layers tightly curled into tubular
structures (dehydra cc ) (Table 4).
Hatloysite exists in nature in both hydrtted and dehydrated forna. It
is hydtated forms that readily adsorb polar fluids and organic cations on
27
-------
interlayer surfaces. However, if water u - ‘.r” nn is lost due to heating
or extraction, the clay takes on the curled tube shape. 1 nce this form of
halloysite (referred to as metahalloysite) is dehydrated, it will not
readily reh ’drate and loses its capacity for adsoption of p lar organic
fluids (MacEwan, 1948).
Exchangeable Cations
Exchangeable rations are positively charged ions that are reversibly
adsorbed to negatively charged clay surfaces (Brady, 1971). Both the
composition of exchangeable rations and resulting equilibrium concentration
of the cations in soil water will greatly affect the permeability of a
compacted clay soil (Marshall, 1959).
Effects of composition of exchangeable rations on permeability of
smectite, illite, and kaolinite are illustrated in Fig. 7. In general, a
clay saturated with divalent caticns (such as calcium) is more permeable
than one sa.:urated with monovalent rations such as sodium (Yong and Warken—
tin, 1975).
Sodium has a large hydrated radius which results in large interlayer
spacing and hence disperses the clay. The dispersed clay pa:ticles are
free to migrate with the percolating leachate, eventually lodging in and
clogging pores, effectively reducing pe . meability. However, if there were
higher salt concertration in a clay than free water to hv4uate the salts,
the effective hydrated radius of sodium and interlayer spacilig between the
clay particles woild decrease. Thus, while sodium—saturate 4 clay will
generally have low permeability, if the concentration of alt , in the soil
were large enough, the clay might not disperse. Without thc dispersed clay
lcgglag pores, soils with excess salts almost always exhit- it permeabili—
ties larger than a soil saturated with sodium but with lower overall salt
content (Quirk and Schofield, 1955).
Calcium has a relati”ely small hydrated radius -d two charges per
atom. These characteristics combine to make calcium— urated clay soils
more resictent to dispersion and generally more permeable than sodium—
saturated clay soils (Yong and Warkentim, 1975). -
While the trend toward lower permeabilities with increasing exchange—
atle sodium levels is sane for all clays, the effect is more pronounced for
smectitic clays (Fig. 7). This is due to the relatively large cation
exchange capacity, specific surface area, and hence capacity to swell of
smectite. Sodium—saturated smectite adsorbs interlayer water to yield
basal spacing from 1 nm (oven dry state) to over 5 mm (Theng, 1979). This
represents a thickness of 4 mm for water on each surface. While this much
interlayer expansion would at first appear advantageous for reducing clay
liner permeability, the expansion is reversible and hence sodium smectite
is susceptible to shrinkage. Another problem with sodium smectite is that
when fully expanded, it is susceptible to dispersion and internal erosion.
When a clay is dispersed, it lacks structural strength and will flow as a
28
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EXCHANGEABLE
I I I I
0
% Na
1 I I
I00
I I I I I I I I I I I
too
% Ca
0
FiG. 7 Effect of the Composition of Cations on the t’ertneabliity of
Clays (Modified from Yong arid Warkentin, 1975)
KAOLIN ITE
Li
1
C-)
U)
0
-J
>-
F —
-J
Li
Li
ILLITE
CATION
I I
29
-------
viscous fiuii. This may cause problems such as loss of ctrength in ..
impoundment sidewalls.
Calcium—saturated smectite adsorbs Interlayer water to yteld stepwis .±
increases in basal sparing from 1 nm (oven dr state) to about 2 r.m (Therig,
1979). ThLs corresponds to a 1 nni thickness of water per surf ace when Ca—
smectite is fully expanded. With divalent rations such as ca ciun or mag-
nesium adsorbed to surfaces, the clay is resistant to welling and disper—
sian. Clay in a calcium—saturated state tends to b : flocculated into
stable aggregates of 10 or more clay particles. These aggregates act as
larger unit particler and thus pores between these unit particles tend to
be larger than pores in a dispersed clay. Formation of these interaggre—
gate macropores is the primary reason for larger permeability of a divalen:
cation—saturated clay.
Waidron and Constantin (1968) found that permeability of sodium—satu-
rated smectites decreased when NaC1 concentration in the percolating leach—
ate decreased. A similar clay saturated with calcium showed no appreciable
decrease in permeability with respect to decrease in calcium concentratIon
in the leacnate. QuirK and Schofield (1955) similarly showed large perme-
ability decrease with decreasing leachate salt con ontration for clays with
higher exchangeable sodium percentages. Hughes (1975) e amined the effect
of a concentrated salt solution (water containing 3.1% NaC1 + 3.6 f Na 2 SO 4 )
on permeability of a clay liner constrjcted f rum a mixture of sandy soil
and sodium—saturated smectite. With a four foot head of water, permeabil-
ity of the clay liner increased 100 fold (from 1.0 x iQ — 6 to 1.0 x io
cm/see) in seven days.
Mcl’ eal (1968) developed a procedure for predicting permeability of
soils containing swelling clays. For smectites in mixed salt solutions for
a given SAR si’fiari adsorption ratios (SAR Na/(Ca + Mg) , where amount of
adsorbed cations is given in mmole;liter), permeability was always found to
be greater at lower SA v 1ues. At given SAR values, the permeability
decreased with decreasing salt concentration of the parcolating leachate.
McNeal and Coleman (1966) evaluated the effect of decreasing followed
by increasing electrolyte (salt) concentration of soils with smectitic
illitic, and kaolinltic clay fractions. They found that permeability of
soils rich in kaolinitic clays were relatively insensitive to decreases or
increases in salt concentration. Soils with predominantly illitic clays
showed moderate decreases In permeability with decreasing salt concentra-
tion and no change in permeability with increasing salt concentration.
Sraeetitic clays showed large permeability decreases with decreasing salt
concentration, and only soils with a large amount of smectitic clays showed
any recovery of initial permeability values with increasing salt concentra-
tions.
FAILURE MECHANISMS OF CLAY LINERS
Failure mechanisms of clay line:s are defined here as any interaction
of the compacted clay soil liner that car . substantially increase its
30
-------
permeability. Climatological cycles (wet—dry, freeze—thaw, percola .ing
rainfall that dissolves soluble clay so-il conponents, etc.) are widely
understooc to be responsible tor much of the structural development and
oermeabili y increases in clay soils (Brewer, 1964; Brady, 1974). dowever,
this text is mainly devoted to investigating a much less understood context
of structural development in clay soils: the inservice environment -of a
remolded and compacted clay soil liner used for hazardous v e landfills
and surface impoundments. Two main failure me h nisms discussed are
dissolution and piping, and volume chanCes.
Dissolution and Piping
Dissolution a: d piping are considered together because their effects
on permeability of a clay liner tend tu be complimentary. As a dissolving
agent erodes pore walls, the- released fragments of soil tend to clog pores
unless these pa’ticle fragnents are “piped’ out of the compacted eiay
soil. Theoretical investigation of clogging have been reviewed by Kovacs
(1981).
Both organic and inorganic acids and bases react with, and many dis-
solve, portions of compacted clay soils. Acids dissolve aluminum, iron,
and silica, eroding the lattice structure of clays an releasing undis—
solved fragments for migration with a percolating leachatc (Grim. 1953).
Acids may also oxidize native organic natter and dissolve calcium carbonate
nodules.
Soluhilitv of silica is affected by a va’iety of environmental factors
and the form of silica. Amorphous silici is more soluble than crybtalline
or polymeric silica. Silica is more soluble at higher temperatures, pres-
sures, and pH’s (Yariv and Cross, 1979). Of course, larger particles of
silica—containing minerals will be sloeer to solubilize due to decreased
surface area. Wey and Siffert (1961) showed that aluminum and magnesium
ions drastically affect solubility of silica in pH ranges of 5 to 10.5 and
10 to 12 ‘respectively.
Silica is also more soluble in the presence of organic acids such as
those found in humic acids (Barnum et al., 1973; Bartels, 1964). Bases
have been shown to extract silica from clay lattice structures (Nutting,
1943). Solubility of silica is pH dependent and greatly ni.reases above pH
9 (Alexanderetal., 1954). Amorphous silica is more soluble than crystal-
line or polymeric sflica, but exact soluhtlity measurements are dIfflcul
due to slowness of equilibria and large solubility effects (Krauskopf,
1956).
Usually pore sizes present in compacted clay soils are not large
enough to transport slaked fragrients produced by reactive acids or bases.
in this case, pore clogging and t least a temporary decrease in per-neabil—
ity of a clay liner would occur. If, however, the clay liner were placed
atop stratum containing pores large enough to “pipe” soil fragments or if
31
-------
clogging frdgmel-lts themselves were dissolved, permeability increases could
evefltually be expected to occur.
Piping has been described as “acriv. erosion of scil from below the
ground surface which occurs as a result of substratum pressure and the
concentration of seepage n localized channels” (Mansur and Keuff:nan,
1956). Jones (19Th) found early stages of piping development to be associ-
ated with vertical contrasts in structure and permeability of soils. Soil
piping was also associated with shifts in soil pore size distribution
toward macropores with no corresponding change in total porosity. A reac-
tive fluid may enlarge surface area of pores by dissolution of the soil
matrix between two pores. While reactivity in a fl”id is reduced by its
action on the pore wall, the size increase in the pore will increase rate
o delivery of the fl’.iid to the pore. In this manrer, any variability In
pore size distribution of a clay liner may be magnified with time. Schech—
ter and Gidley (1969) found that wormhole formation was the result of a
reactive fluid preferentially flowing in larger pores. They further found
that quasi—equilibrium was reached where further growth of a pore ‘.as
limited by the rate of difiusion of the reactive fluid.
Mitchell (1975) found that quick clays were often asso .iat d with
the presence of organic compounds possessing strong dispersing characteris-
tics. These clays act as viscous fluids with no structura’ st ength a:id
are thus susceptible to erosion caused by seepage. Reservoir water seeping
into earthen dams nas been reported to cause dispersive piping ar.d eventual
tunneling all the way through the dams. Tunneling was reported to occi ’r in
soils with a local permeability of greater than 1 x cn/sec.
Similarly, differential solution and subsequent .eaching has been
reported to result In formation of channels, sink l’oles, and cavities
(Mitchell, 1975). This was foun. 1 to be especially true with calcareous
sediments. Cedergren (1967) reported that diffetentlal leaching of lime-
stone, gypsum, and other water soluble mineral croponents could lead to
development of solution channels that increase in size with tine and
substantially increase permeability.
It is important not to underestimate the importance of minor soil and
geologic detail on permeability of soil formations. Cedergren (1967) found
that such minor details caused the majority of failures in dams, reser-
voirs, and other hydraulic structures. Furthermore, he concluded that most
failures caused by seepage could be placed in the followis g two categories:
1. Those caused by soil particles migrating to an escape exit resul-
ting in piping and erosional failures;
2. Those caused by uncontrolled seepage patterns leading to satura-
tion, internal erosion, and excessive seepage.
Crou’h (1978) found that tunnels and tu : nel—gullies (or pseudokarsts)
developed in dispersive soils where soll—collold bond strengths were low
compared to energy of water flowIng through the soil. He found that
dispersive soils or those with low structural stability were associated
32
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with tunnel eroricti throughout the world. Other factors found to ba
related to tunnel erosion were Exchangeable Sodium Potential (ESP), soil
cracks, low permeability, and hydraulic gradients.
In a study of variables affectI ’g pining, Landau and Altschaeffl
(1977) noted strong interaction between chemtcal coaposition of eroding
water and compaction water content, Ion concentration seemed to have
little effect on soil piping susceptibility for mixed illitic and kaolini—
tic clay loam compacted dry of optimum. For ihe sane soil compacted at of
optimum, soil piping susceptibility was highly related to ion concentration
in eroding water. The authors suggested that wet of optimum compaction
produced more parallel orientation of soil particles which increased the
effect of osmotic repulsion. Consequentl.’ the ion concentration of oi1
water would have a relatively greater effect on dispersive forces in soil
compacted wet of optimum. When low ion concentration eroding eater was
combined with wet of optimum compaction, they reported an exceptionally low
resistence to internal erosion. These findings are felt to be especially
important due to the long standing practice of compacting clay liners wet
of optimum to produce minimum ir.itial permeability possible for a given
compactive effort.
Piping involves slaking soil particles. Slaking is defined as disin-
tegration of unconfined soil samples when submerged in a fluid. Moriwaki
and Mitchell (1977) Livestigated dispersive slaking of sodium and calcium—
saturated kaolinite, illite, and smectite. All, the clays slaked by disper-
sion when saturated with sodium, with the process proceeding faster with
sodium kaolinite and sodium illite. Sodium illite swelled slightly. while
dispersion of sodium smectite was preceded by extensive swelling. Sodium
kaolinite underwent no visible swelling while dispersing. For CalCiUm—
saturated clays, illite dispersed much more slowly while the rate of
dispersion increased for kaolinite and smectite. Calcium kaolinite was
thought to disperse faster because of its higher permeability relative to
sodium kaolinite. Sodium smectite was thought to disperse slowly because
of the large degree of swelling it underwent. This would lower per abil—
ity, thus slowing water entry and retarding dispersion.
Compaction has been shown to decrease the electrolyte content of
expelled interlayer water Rosenbaum, 1976). Such lowering of fluid elec-
trolyte concentrations in sodium—saturated clays may cause substantial
swelling and dispersion (Rardcastle and Mitchell, 1974). This dispersion
causes parti:le migrations. If there were fluid—conducting pores large
enough to transport these dispersed clay particles, permeability increases
and soil piping might result (Aitchison and Wood, 1965). It is ir nortant
to note that piping would initiate on the underside of a clay liner where
clay particles can migrate into substrata containing larger pore diame-
ters. The soil pipe would then progress upward through the clay liner
until it found an opening into the impoundment. Since clay particles have
been shown to migrate through porous media containing less than 15 clay
(Hardcastle and Mitche1 , 1974), clay liners underlain by soils containing
less than 15% clay may be susceptible to soil piping.
33
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Fouc laboratory tests for the determination of soil, sjs c tib lity to
dispersive erosion have been developed by the U. S. Soil ¶ unservatiOn
Service. A major conclusion of a recent symposium on soil piping was that
these four tests should be performed on soils where piping can cause
unacceptable damage (Sherard and Decker, 1977). The four tests (AST I
Special Technical Publication Number 623) are the pinhole test, a test of
dissolved salts in pore water, the SCS dispersion test, and the crumb
test. ideally, the tests should incorporate both primary and secondary
waste leachates.
Volume Changes
Volume changes occur in clay soils from bulk and interlayer shrink-
age. Bulk shrinkages are usually identifiable by visual inspection of a
clay liner. This type of shrinkage is represented 1w macrostructursi
features such as cracks, fissures, joints, faults, slickensides, shears,
channels, ice wedges, planes, and chambers. l iterlayer shrinkages may not
be detected by visual inspection, but their inpact on permeability of a
cl ;y liner can be just as dramatic. This type of shrinkage is represented
by microstructural alterations in the clay liner which are usually mani-
fested as shifts in pore size distribution. An extensive review of voids
in soil that result from bulk and interlaniellar stiri-kage has been written
by Brewer (1964).
Volume changes in clay liners cccur when there is a change in water
content of clay. Adsorption of water on exposed surfaces occurs with all
clay minerals, with the exception of completely dehydrated halloysite. For
a given change in water content, the magnitude of volurre change is depend-
ent or, clay mineral type, arrangement of clay particles, size of clay
particles. surface area per unit weight of clay, and kind and proportion of
cations adsoroed to clay. Smectite, and to a le’ er degree illite, ‘nay
cause problems associated vith changes in volume o clay liners (J:able 4).
Two contracted lattice sheets of smectitic clays have a 2 nm thick-
ness. Since each layer of adsorbed water is ar proximately 0.25 mm thick,
the adsorption of foar water layers on each of the two external and inL - r—
layer surfaces would give a smectitic unit particle (2 clay layers) n
increase in volume of 200Z between the dehydrated and hydrated states. l
is the small size and expandable lattice properties of the smectitic unit
particle that give this clay its uniquely large potential for volume change
(Theng, 1979).
Extraction of interlayer water causes shrinking and associated crack—
1mg exhibited by smectitic soils (Bayer, et al.,1972; Grim, 1968). Crack-
ing is a result of the clay undergoing three dimensional shrinkage. Where
the rate of watcr extraction is not uniform, cracks will form in wetter
soil (Yong and Warken ir., 1975). Water content of a clay liner r ay change
if an organic leachate extracts water from the clay liner.
34
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Shrink—Swell Be avtor
Swelling behavior of compacted clay soils has been shown to be related
te clay c inerals present (Yong and Watkentin, 1975), presence of organic
connounds adsorbed to clay surfaces (Hughes, 1975, Rar ier, 1978),
e changeahlc cations present (Norrish, 1954), fabric or structural arrange-
ment of clay particles (Lambe, 1958a, 1958b), overburden pressure (Davidson
and Page, l956), and Attarberg limit values of clay soils (Holta aad Gibbs,
19i6). Swelling tends to decrease permeability of clay soils, hut 3iOul—
taneously indicates potentIal for shrinkage shoull the soil environment be
alter.2d “hscantiaily.
gweilieg behavior of clays is significantly affected by the clay
minerals presc t . (Table 4). Both kaolinite and illite have substantially
less capacity to we11 than smectltic clays. Halloysito has a shrink—swell
potential between that of kaolinite and illite.
Smectite owes its Jarge shrink—swell capaciti to a combination of Its
lar e cation exchange capacity, moderate surface charge density, octahedral
iay : tsc.morphoun substItution, and large sur ’ace ar a to volume ratio
(Casc, 979). With larger population of exch n eable ations, there will
be A co’ respondtngly larger potential volurietr c increase upon hydration of
the ca1i mr. . moderate surfa e charge density leaves more clay surface
area for water adsorption and allows more water of hydration to be posi-
tioned between the cation and the clay surface.
in smectites, the octahedral lattice sheet is sandwiched between two
tetrahedral lattice sheets, and cost somorphous substitution occurs in the
octahedral That is, substitution of Mg or Fe in the octahedtal
lattice pos ticns nocmally held by tU- gices sr ectitic clays a net nega—
tue charge. Furthermore, since the negative charge emanates [ rca the
middle of the lattice structure, t ie electrical charge is diftuaed or
evenly spread over the entire clay surface. The diffuse nature of the
negative charge plus the relatively small charge densIty of smectites
decrease the rigidity with which exchangabie positively charged cations
are held to the clay surface. This permits formation of a wide, diffuse,
electrical double layer. The repulsive forces between adjacent cation—
covered positively charged double layers enable the monovalent saturated
smectites to continuously swell until one of the following oLcurs:
1. Repulsive swelling continues until all remaining attractive
forces are overcome, and the clay disperses into Individual
particles forming a gel., sol, or suspension (Theng, 1979).
2. Confinement pressure of the surrounding clay soil body prever ts
further swelling (Lambe and Whitman, 1979).
3. Swelling causes a shift in pore size distribution toward larger
number of micropores and smaller number of macropores (Lauritzen
and Stewart, 1941).
35
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Since smectites have a large surface area to volune ratio which cives
the clay approximately 800 m 2 /gn available surface to unich water can
adsorb, this large amount of adsorbed water represents a large potential
for shrinkage or swelling (Thei g, 1979).
An inpotant aspect of the shrink—swell be1 avior of kaoliaite and
illite is that these clays shrink upen dehydration hut show v ry little
swelling upon subsequent rewetting (Tong and Warkentin, 1975). This
characteristic limits the oapacity for these two clays to “self heal” or to
close shrinkage cracks once formed.
Smectitic clays have a large and reversible capacity for volume
changes under normal conditions. Howe ’ei, Gieseking (1939) found that
smectites lose their capacLy for “self healing” or swelling when exposed
to organic cations. Barriar (1978) reported the swelling ot smectites
after exposure to neutral polar organics (alcohols, glycols, ketoncs, and
acetonitrile) and neutral nonpolar organics (xylene and cyclopentane).
Watson (1968) found that certain concentrations of surfactants stabilize
soils against dispetsion and swelling, thereby preventing a decrease in
permeability of a soil. Hughes (191.) found that one reason nr reversal
of swe .ling in smectites was adsorption of organics on clay surfaces. He
suggested that adsorbed organics interferred with the interactions between
int’rlayer water and clay surface. Grin (1968) found that water adsorbing
propei :les of smectitic clays were reduced as interlayer spaces were coated
by organic cations. He noted that “in gmeral, the larger the organic ion,
the greater is the reduction in the w ter a(lsorhing capacit’. Grin et
al., (1947) also found that the water adsorptfon capacity of kaouinitic
clays were reduced following treatment with organic cat .ons. The decrease
in water adsorption was less than the decrease exhinited by stuectitic
clays. Grim (1968) soruned that the water adsorption decrease for other
clays would be intermediate etween those for smectite aiid kaolinite.
Hughes l975) found that exchangeable cations could affect the swell.
behavior of alay soils in rt least two ways, as follows:
I. Exchange of monovalent cations for divaleat cations could cause
reversal of swelling.
2. Presence of e’cess sodium could cocipete for available water with
clay surfaces causing a decrease in interlayer spacing of the
clay.
Norrish (1954) showed initial or crystalline swelling of clays to be
directl ’ related to hydration energies of interlayet cations. Crystalline
swelling has beer. defined as the swelling range at which “the gross crystal
morphology is preserved” (Theng, 1979). Within this range of water con-
tent, swelling pressure exhibited by clay minerals is largely determined by
exch ’ngeable cations (Norrish, 1972). Above the water content range of
crystalline swelling, the valence of the exchangeable cation controls the
swell behavior of snectitos.
36
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Monovalent cation—saturated smectites will generally continue to swell
beyond the crystalline raii e into state Ii or osmotic swelling (swelling
due to the migraticr. ot- wa cr to higher salt conce tration in interlayer
water as compared to Interpodal or irttaraggregate water). The consistency
of smectite in thia state ranges from that of a still paste at the low end
of water content range (“-0.7 ge H- O/gm clay), to that of a tnlck gel at the
high end of the scale ( 2 ga d 9 0 /gm clay) (Theng, 1979).
Soil fabric or strtcture has been defined a ; the physical constitution
of a soil material as expressed by the spacial srrangement of the clay anc
other solid particles and associated voids. Of special importance in clay
soils are the extremes of possible spacial arrangements of clay particles
from the flocculated structure (edge to face) to the dispersed structure
(face to face). Clay soils with a dispersed structure will tend to undergo
more vclumetric shrinkage with changes in water content (Lambe, 1958a).
The degree of dispersed structure (parallel orientation) exhibited by corn—
pacted clay soils Licreases as water content of the soil or compaction
effort are increased (Fig. 8) (Lambe. 195gb).
Structural form affects permeability as well as swelling behavior of e
compacted clay soil (Mitchell and Hooper, 1965). The flocculated structure
essoci Xed with compaction on the dry side of optim m moisture results In
larger average pore diameters and permeabilities than exhibited by clay
soils compacted at water Contents on the wet side of optimum (Fig. 8). In
etthei case, Mitchell (1975 concluded that compacted cl ys revert to n..re
flocculated structure after placement and hence may exhibit a several fold
increase in permeability with tine.
Another factor which influences clay liner swelling and shrinking
potential is overburden pressure. Swelling pressure in clays will, deter-
mine the extent to which it is capable of swelling undor a given overhuruen
pressure. Davidson and Parc (1956) determined that swelling pressure
exhibited by sodium saturated mineral samples of smectite was substantial,
wh1e that exhibited by kaolir.1te and illite was negligible.
Swelling pressure exert’ d by smectites in the crystalline swelling
state ( ‘uO.O—O.l gm H 2 O’gm clay) is approximately io —io dyne/cm 2 . Th
opposing forces generatlig this net swelling pressure are catioa hydration
(repulsive) and electrostatic attraction (Norrish, 1972). Hence. swelling
pressure in this state is largely determiner by hydr.t’tion energy of the
cation, and would he expected to decrease with increasing cation valence.
Consequently, smec:titcs saturated with divalent cations do not normally
swell past the “-‘2mm interlayer spacing limit of crystalline swelling
(Theng, 1979). In other words, interlayer repulsive force of cation hydra-
tion is less than both van der Waals forces of attraction between adjacent
clay sheets and electrostatic attractions between divalent cation and nega-’
tiv ly charged clay surfaces. Clays satur,ted with ntoi ovalent catlons
continue to exert a net. swelling pressure (10 —1C dyne/cm -) at interlayer
spacings greater than 2mm with water contents from n O.7—2Ogm H 2 O/gm clay.
Net swelling pressure at these interlayer spacings is due to the following
two opposing forces:
37
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Co npactws
I
1 1G. 8. Effects of Compaction Water Content on the 5tructural
A rnagement of Clay Minerals (Lanbe, 1958b)
1. Repulsive, osmotic forces of interacting d f fuse electrical
double layers (i.e., mutual repulsion of cation rich hydration
shells surrounding adjacent clay sheets);
2. Frictional forces generated by e ige to face bonding of the clays
and, to a lesser extent, van df r Waals attractive forces (Theng,
1979; Norrish, 1972).
Potential for volume changes it a clay also can be significantly rela-
ted to Atterberg limit values such as the “plastic range” and “shrirkage
limit” of the clay (Holtz and Ci bs, 1956). The “plastic range” is the
range of water content below whicn a clay will lose its cohesiveness. The
shrinkege limit” is the w tet con entof a clay below which no further
shrinkage is possible. V lues for ktterberg limits are given for clays
with low, medium, :ind high s iell potential in Table 5.
COKIIp3CtiVS Effort
D
A
I
I
38
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TA;LE 5. SWELL E’OrENTIAL VERSUS ;.TTERBERC LIMIT VALUES
IN TIWEE CLAY SOILS*
Such
Potential
Low
Medium
High
Plastic
range 1
<30
30—50
>50
Shrinkage limit 1
>12
10—12
<10
* After Holtz and Cibbs (1956)
Water content as percentage dry weight
Sw ling bcraiior in clay soils is a complex result of many nterac—
ting mechanisms. Bowles (1979) four d swell behw;ior of soils to be related
to clay type, overburden pressure, void ratio. method of saturation, and
general environmental conditions. Franzm i r and Ross (196 ) reviewed
factors affecting swell pctential of 30 kaolinit!c, Illitl.c, and smectitic
clay soils. They found swell potential of clay soils to be most signif —
cantly related to kind and anonnt of clay and soil fabric (expressed as
amount of clay per unit dry v lunc of soil).
A recent review oF the shrinking and swelling heha ’ior of clay soL1 ;
has teen written by Brown (1979). The review extensively discusses
shrink—swell behavior relating tc swelling pressure, Atterberg li nits,
structure, strength, stabilization, water holding capacity, and permeabil-
ity of clay soils.
Interlayer Spacing Changes
Interlayer spacing of clay minerals refers to spacing between adjacent
basal surfaces. This includes the thickness of one clay layer pius tne
thickness of the borbed fluid layer getween tw’ adjacent clay layers.
Changes in interlayer sp icing of clay may inpact its bulk volume, pore size
distribution, and thus pt±rmeability. Factors affecting this spacing
include the clay mineralogy, properties of the fluid, and the exchangeable
catlons adsorbed to the clay minerals. A related phenomenum, applicable to
all solid surfaces in clay liners, is the change in thickness of the fluid
films coating soil particles and lining soil voids.
In the service environment of a compacted clay soil liner, nearly a t
accessible clay mineral surfaces are water—wet. Two significant exceptior.
are clay surfaces coated with naturally occurring hydrophobic substances
and the fully dehydrated form ot hahloysite. The tollowing discusslo
emphasizes interlayer spacing changes that may Occur in initially water we
clays or dehydrated clays exposed to water and organic fluids simultan-
eously.
39
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Effect of Clay M neralov. Clay minerals exhibit Interlayer spacings
that reflect strength ot bonding between adjacent clay iaycLs. the
expandable clay minerals (illite and kaolinite) only rareiy undergo inter—
layer spacing chances due to strength of riterlayer bonds. xpandable
lattice clays (smectites and to some extent ha iloysite) have much weaker
interlayer bonds and thus are able to intercalate (adsorb between adjacent
layeta) water and a variety of polar or cationic organic fluids.
Smectites are by far most geographically videspread of the exoandable
lattice clays. Due to the large hydrated radius of monovalent sodium,
snectites saturated with this catfon adsorb water until the clay disperses
into a clay—water suspension. At this point, the water layers are several
times the thickness of the clay layers (Theng, 1979). Lu the case of
divalent cations, interlayer expansion is normally limited to the point
where water layers are about equal to the clay layers in thickness (Theng,
l 79: Grim, 1968). This is caused by strong electrostatic attractions
batween negatively charged clay sheets and the two positive charges on the
divalent cat o (Theng, 1974).
Another property of clay minerals that affects interlaver expansion is
interaction bctween interlayer cations and dipoles present on the clay
surface. Caticr.—dipole interactions have been found to dramatically affect
interlayer spacings of homoienic snectites with acetone and ethanol
(Bissada et a ’., 19b7). Iriterlayer spacing increased with cation sequence
; + < a
-------
Water .a.-i be displaced from saturated 1ay soil by movement of an
organic fluid luto the soil. As the organic fluid mo:es througn a I lufd—
co: ducti g pore, incompressible water is displaced. By itself, this does
nat change ;nterlayer spacing, but the new pore fluid may cause mevement of
water from ncn—cr ndizcting pores and interlayer spaces to satisfy equilib-
rium water content o the IntrudiLg organic fluid. Since water lu usually
adsorbed to clay surtac s in u1tiple layers, the most tightly adsorbed
surface layers o water need not be renlaced for there to be change in
laterlayer spacing.
Water disolac-.%nent would first affect Interlayer spacing ci clay
partIcles iumedi.:tel adjacent to or lining pores through which organic
fluids were moving. With a compacted clay liner, water would be expected
to move from other pottens f the liner to re—establish eqoilibriun inter—
layer spacing that previously existed in the clay soil. However, I inter—
layer spacing changes in clays coatiag or adjacent to pores also caused
structural rearrangement of clay particles, changes in icterlaver spacing
might be irreversible.
TABLE 6. 1NTERLAYER SPM INGS OF CLAY MINERALS WITH WATER
A THE A1 SORBeD FLUID PH SE*
Clay !neral
Exc 1-ap abI cC,tion’ ___
Li
Na
Ca
Soectite
.
2.20
1.90
i.9 )
1.9 )
Illite’
1.43
1.43
Kaolinitc 2
0.72
0.72
0.72
0.72
Hal loys ftc
(Hydrated )3
1.01
1.01
1.01
1.01
* Brown (1961)
X Monovalent cations may result in extensive interlayer swelling beyond
the values given
Normally potassium is non—exchangeably adsorbed yicldin an interlayer
spacing t f Inn.
2 protons are usually the intertayer cations since hydrogen bonding pre-
vents interlayer separation
Meta ialloysite (deh drated) yields interlayer spacings approximating that
of kaollnlte
41
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A combination of interlayer spacing decrease and particle rearrange—
ment by organic fluids could cause change in effective pore diameter and
hence overall permeability of the clay. A factor of 4 increase in a fluid
conducting pore diameter Is depicted in F Ig. 9. Such increase in pore
dIameter would increase permeability by a factor of 256.
If the intruding orgar .ic fluid had an appreciable dipole moment, the
amount of water solubilized would be greater th in if the fluid were non-
polar. However, polarity a’so gives the organic fluid ability to directly
replace water in Interlayer spaces. This effect would negate some inter—
layer spacing decreases expected from removal of Lmterlayer water.
Water can be rericcee in capillary pores (micropores), interJayer
spaces, and interlay r surfaces by cationic and strongly polar organic
fluids. The strength of the water retention by clays is determined by the
hydration energy of interlayer cations, adsorption energy of the water on
interlayer surfaces, and ability of water to brIdge across capillary pores
by a network of hydrogen bonds. Water could be replaced in micropores and
interlayer spates by disruptIon of streturing generated by the network of
hydrogen bondt . If this occurre , resuting interlayer spacing of the clay
would ‘e a ccmplex function of several interacting fluid properties affect-
ing the balance of attractive and repulsive forces between clay layers.
Forces of attraction, represented by the London—van der Waals forces,
are strongest close to the clay surface and diminish rapidly with increas-
ing distance form the surface. Values of these attractive forces at given
distances from the surface do not “ary significantly with chenges in envir-
onmental context. An explanation of theory underlying this force has been
written by Van Olpherm (1963).
FIG. 9. Change in a Pore Diameter (400%) Corresponding to a
Permeability Increase of 25,600%
42
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Forces of repulsion between clay layers are deter ained by several
factors such as salt concentration, dielectric constant, and dipole moment
of the fluid in the interlayer. Effects of salt concentration and dittec—
tric constant on repulsive forces are schematically represented in Fig.
10. Weiss <1958) noted the direct relationship between salt concentration
and interlayer spacing of smectites in a study utilizing distilled water
and several concentrations of sodium chloride in water. Both distilled
water and U.OJN Ned gave infinite thterlayer spacing values (The clay was
completely dispersed), while 1.0, 3.0 and 5.ON NaCl gave interlayer
spacings of 1.92, 1.60, arid <1.57 rim respectively. Yong and Warkentin
(1975) found that at interlayer spacings less than 1.5 na, attractive
forces between clay particles were greater than the repulsive forces. As
the concentration of salt dissolved in the iriterlayer space increases, the
repulsive forces (represented by thickness of the electrical double layer)
are diminished. If the salt conc ntratiori iri an interlayer fluid is high
enough to cause the attractive forces to exceed the repulsive forces
between clay particles, the clay will tend to flocculate. This could
change a dispersed, structureless, and slowly permeable clay soil into an
aggregated, structured, and more permeable one.
An analogous situation could occur where interlayer water is displaced
by an organic fluid that has a lower dielectric constant than water (Figure
10). Theory of dielectric constant has been thoroughly explained by
Bockris and Reddy (1970). Simply stated, the dielectric constant repre-
sents the ability of a fluid to transmit charge through it eif. As this
ability decreases (i.e., decreasing dielectric constant), the fluid film
surroundin the clay and containing positive canons must he thinn r for
the negative surface charge on the clay to be neutralized.
Due to the effects of dielectric constant or’ the electrical double
layer, there is a relationship between the dielectric constant of an
adsorbed fluid and Interlayer spacing exhibIted by clay particles. ln
general, interlayer spaci.ig decreases with decrease in the dielectric
constant (Table 7). This apo . rent relationship is complicated by a number
of other factors such as the dipole ioment of a fluid (Barshad, 1952),
interlayer cation of the clay (Bissada et al., 1967), degree of nethyl
substitution on the organic molecule (Olejnik eta!., 1970), and ion—dipole
interactions (Czarnecka and Gillott, 1980). Most studies of various
factors affecting interlayer spacing, ho ever, have been limited to situa-
tions dealing with cla’, surfaces following pretreatments such as dehydra-
tion prior to iminetsior in. test fluids (Barshad, 1952).
In one study that has some applicability to hydrated systems, the clays
were dehydrated prior to the study but then immersed in a mixture of water
and an organic fluid (Barshad, 1952). The dehydrated clays were immersed
in 100% water and various mixtures of water and propanol to obtain inter—
layer spacing for the clay ‘xposed to a fluid series with decreasing
diele.tric constant (Table 8). As predicted, interlayer spacing exhibited
by calcium saturated sinectite decreased with decreases in dielectric
constant of the fluid mixture. The same author performed a similar study
obtaining similar results with water—glycerol mixtures.
43
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FORcES
OF
REPULSiON
FORCES
OF
ATTRACTION
A
B
C
DISTANCE BETWEEN
ADJACENT CLAY LAYERS
AQUEOUS SYSTEM
(SALT
HcEt4TRAT1O$L
ORGA dIC FLUiDS
(D(ELEC R IC
CO 14STAN11
HIGH
LOW
MEDIUM
ME UM
LOW
HIGH
FIG. 10. FOL CeS Between Clay Surfaces as Affected by Salt
Concentration and Dielectric Constant
TABLE 7. INTERLAYER SPACING OF CALCIUM SMECTITE AS A FUNCTION OF
DIELECTRIC CONSTANT AND DIPOLE MOMENT*
Interlayer
Sorbed
Fluid
Dipole
Moment
Dielectric
Constant
v.99
Benzene
0
2.3
0.99
pøraffin
0
2.)
1.45
Butanol
1.6
17.7
1.70
Ethanol
1.7
25.0
1.11
Methanol
1.6
32.4
1.73
Methyl Ethyl
Ketone
2.7
18.9
1.92
Water
1.8
78.5
From Barshad (1952)
* AU samples were dehydrated at
fluid.
250°C prior to immersion in the test
It
44
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TABLE 8. INTERLAYER SPACING ( ‘F CALCIUM S 1ECTITE+ IM RSED IN FLUIDS
0 ’ VARIOUS FJTELECTRIC cONSTANrs*
Immersion Liqu: d
Dielectric
Constant
(25 °c)
Interlayer
Spacing
(nm)
100% water
78.5
1.92
70% water—30% propanol
57.7
1.88
40% water—60 propanol
36.4
1.84
30% warer—7 1 i% propanol
30.7
1.77
20% water— O% propanol
26.1
1.77
10% water--90Z propanol
22.?
1.52
IOO propanol
20.1
1.44
100% water
lb.5
1.92
40% water—60% glycerol
59.4
1.79
100% glycerol
39.2
1.68
* Modified from Barshad (1952)
+ Dehydrated at 250CC prior to immersion in liquid.
The dipole moment of a fluid lsc affects interlayer spacing by
affecting the number of fluid layers tiut will form on clay surfaces.
MacEwan (1951) found that the number of fluid layers in smectites increased
with iicreasing dipole moment and decreasing molecular size. Strongly
polar fluids, such as nltromethane and aceeonitrile 1 were fcund to form
more than two layers (MacEwan, 1948).
While interlayer spacing resulting from intercalation of given
compound increases with increasing molecular size 1 the number of fluid
layers that will adsorb to a clay surface decreases with increases in
molecular size. This phenomenum explains the initial increase in inter—
laytr spacing from methanol through ethanol which are small enough to
adsoLb in two layers (Table 9). However, members of the homolt gous series
larger than ethanol are restricted to adsorbing in one layer. Thus from
ethanol to propanol, there is an initial decrease in interlajer spacing
corresponding to one adsorbed layer. Followlrg this initial decrease, the
interlayer spacing gradually. increases with increasing molecular size of
the adsorbed alcohol. The decrease from two to onc adsorbed fluid layer is
due both to the increase in molecular size and the decrease in dipole
moments and dielectric constants of the large alcohols.
In comparing che interlayer spacings for an organic fluid adsnrbed at
different dehydration temperatures (Table 10), several interesting trends
can be observed. Dehydration at higher tempcratures removes more of the
45
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TABLE 9. CHANGES OF INTERLAYER SPACING IN SMECTITE WITH A HOMOLOGOUS
SERIES OF NORMAL MONOFI? URIC ALCOHOLS*
Normal Mor ohydric SpacIng Between Thickness of
Alcohols Layers One Layer
(nni) (em)
Number of
Adsorbed
Layers
Methanol 1 0.74 0.37
2
Ethanol’ 0.79 0.39
2
1-Propanol 2 0.45 0.45
1—Butano l 2 0.46 0.46
1
1
1—Pentano l 2 0.46 0.46
1
Z—Methyl--2- -Butanol 2 0.54 0.54
1
Cyclohexanol 2 0.54 0.54
i
* From MacEwan (1948)
Treated with large excess of cold liquid
2 Boiled down to half ‘ olun e with excess of liquid
TABLE 10. INTERLAYER SPACINGS FOR ORGANIC FLUIDS AT
(PRETREATMENT) DEHYDRATION TEMPERATUR S*
DIFFE ENT
In terlayer Adsorbed Dipole Dielectric
Spacing Fluid Moment Constant
(nm) (debyes)
Dehydration
Temperature
(°C)
250
0.99 Paraffin 0 2.1
1.45 n—Butanol 1.66 17.7
250
1.45 Paraffin 0 2.1
20
1.52 n—Butanol 1.66 17.7
20
1.92 water 1.84 78.5
250
* From: Barshad (1952)
strongly adsorbed interlayer water. Subsequent treatment with orgac ic
fluids yields lower interlayer spacings for clays dehydrated at the highest
temperature. This is also true, but to a lesser degree, when sodium rather
than calcium Is the interlayer cation. When clay is dehydrated at roo n
temperature (20°C) there is still water coating its surfaces. However,
both a neutral polar compound, n—butanol, and a neutral nonpolar mixture,
paraffin, reduce interlayer spacing of clay dehydrated at 20°C as compared
to clay treated with water after dehydration. This indicates that even
46
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compounds less attracted to clay surfaces than water can displace sor e
interlayer wat:er . nd thus decrease interlayer spacing. Such common
neutral nonpolar organir solvents such as xylene, benzene, heptané, or
paraffin oil hive potential for decreasing interlayer spacings in clay
liners.
Concentration of organic compounds in interlayer spaces of clay has
been found to affect preferred compound orientation and hence resultant
interlayer spacing. In a study conducted with fully hydrated smectite,
Greene—Kelly (1955) found that the slightly basic aromatic compound ar.iline
adsorbed with aromatic rings parallel to the clay surface at low concentra-
tions (0.62 meq/gm clay) resulting in low interlayer spacing (1.42 mm).
Orientation of the aromatic compound became perpendicular at higher :oncen—
t:atic is (0.91 meq/gm clay) and resulted in higher interlayer sacings
(1.78 nm).
Assessment of effects of organic fluids on initially water—uet clay
in clay liners is complicated by the complexity of interactions between
clay surfaces and resulting interlayer spacing changes. An increase in
energy is required to dehydrate the clay surface (Gb), repel water from the
interlayer space (Gp), and dissociate an organic fluid molecule from otter
organic molecules in thu flowing phase (Gd) in order to enetra e to the
clay surface. However, energy is decreased when the organic flui is
adsorbed by the London—van der 1laals forces (Gs) or associare with the
exygen on the clay surface (Ga). Such energy derreases wo’ild lacrease the
likelihood of aa organic molecule penetrating the inner Helrholtz layer
(V , which is the layer immediately adjacenr to the surface of a clay.
Pen trrinn of the inner Helnholtz layer by an organic cation is
promoted by a increase in molecular charge (1) or an increase in ilmer
Helr holtz el t ical potential (Y). Regardless of type of orgLctic fluid,
its ability to penetrate to the surface of a clay is greatly enhanced by
increasing its conce.itration (X). An equation relating the above vari-
ables, temperature (T), and the Holtzmenn constant (k) has been given by
Yariv . nd Cross (1979) as follows:
V = Xexp—(YZ + Ga Gs GdAGhLGp)fkT
It is next to impossible to guantitate several, of the. above variables even
in carefully controlled laboratory experinents. Obviously, the task would
be even narder in th actual environment of an in—place clay liner exposed
to a complex mixture of organic compounds. One important factor that can
be gleaned from tho equation, however, is that potential for inner Helm—
ho’:z layer penetration by organic molecules normally excludes prom clay
surfaces is greatly enhanced if the molecule is in high concentration.
The reason for concern about changes in interlayer sp:icing of clay is
the impact the changes may have on permeability of a clay liner. No
47
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studies bav been found that examine the relat onchip between interlayer
spacing and permeabiiity flo iever, by combining information found in
several studies, a relationship can be deduced. Decreasing dielectric
constant or dipole moment of an adsorbed fluid nas been found to decrease
interlaver spacing of clays (Barshad, 952) and yield a clay with increased
permeability (M.ichaels and Lin, 1954).
PERMEAgIL1TY MEASUREMENTS OF CLAY SOILS
Permeability (K) describes the rate at which a fluid car, move through
a porous matrix (Fetter, 1980). Darcy (1856) was first to systematically
study the relationships between flux of a iiqu d through a porous matrix (J
in cm 3 cn 2 sec 1 ), volumetric liquid flow (Q in cm 3 sec’), t e hydraulic
gradient (H), cross sectional area of liquid flow (A tn cm ’), and the
permeability constant for a given po’:ous matrix (K in cm sec’). These
parameters are related through Darcy’s Law:
J= KH
Hydraulic gradient (H) is defi ed as the ratio of the difference in
hydraulic head between the top and bottom oi the porous matrix (t h in cm of
H 2 0), and the length of the poro a matrix over which the liquid flows (1 in
cm). This infers that volumetric liquid flow (Q) is proportional to the
difference tn fluid head (! h) and inversely proportional to flow length (1)
where flow is laminar. Hydraulic gradient (H) can he expressed as follows:
H h (top)—h(bottom ) — Lh
I 1
Volumetric liquid flow (Q) is siuply volume of liquid (v in c 3 ) which
moves through the porous matrix In a given time (t in seconds), and
expressed as follows:
Q=.
Combining the abovn variables, the permeability constant of a porous matrix
can be expressed as follows:
vi
K - A t h
To normalize the permeability constant (K) for flow of fluids th
various viscosities C U expressed as gm cm sec’) and densities ( in gm
the intrinsic permeability constant (k in cm 2 ) can he calculated
from the permeability constant (K) of a porous matrix as follows:
pg
48
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where g is the gravitational constant of 983 cm sec 2 . The viscosity
parameter normalizes resistence to flow of a fluid due to cohesiveners,
while the density paraucter normalizes the effect of gravity. As the above
equation indicates, permeability of a porous natric is directly proportion-
al to density and inversely proportional to viscosity of the permeant fluid
(Fetter, 1980).
One assumption of 1 arcy’s Law is that fluid flow is laminar rather
than turbulent (8ear, 1972). Bowles (1979) stated that turbulent flow
would occur in pipes ahr ”o iydtau ic gradient of 2,100, and in presumably
sandy sour at hydraulic gradients as low as 300—600. Hubbert (1956) stud-
ied flow in a bed of cylinders and found that Darcy’s Law broke down at
hydraulic gradients greater than 600. lIe found the “cause of the failure
of Darcy’s Law is the distortion that results in the flowlines when the
velocity is great enough that the inertial force becomes significant.”
Rumer (1964) concluded that “the limit of validity of Darcy’s Law is not
because of the inception of turbulence but is due to the increasing influ—
ence of the inertia forces.” There inertial forces become significant
before flow is turbulent in the nonlinear laminar flow regime.
The use of large hydraulic gradients has shortcomings. The thickness
of immobilized fluid films on soil particles would be substantially
decreased at large pressures (Yong and Wa:kentin, 1975). This would
increase effective pore diameter available for fluid flow and thus peniea—
bility. On the other hand, large hydraulic gradients can increase soil
particle migration causing soil clogging and a resulting decrease in perme—
abilit’ (Olson and Daniel, 1979).
Criteria for selecting an appropriate hydraulic gradient greatly
depends on proposed use of the permeability study. Where the objective is
to est mate field permeability values, it has bee i suggested “to use gredi—
ents as close to those encountered in the field as is economically feas—
ible ’ (Olson and Daniel, 1919). Zimmie et al. (1981) suggested use of
hydraulic gradients het een 6 and 20 for laboratory studies attempting to
duplicate field cor itions.
In comparative permeability studies, larger hydraulic gradients may be
used. Care should be taken, however, to maintain linear laminar flow and
monitor for particle migration. Comparative studies often use permeant
fluids that may change permeability of a soil (Michaels and Lin, 1954).
Hydraulic gradients used should be far enough below the turbulent flow
thresh3ld to maintain lianar laminar flow after permeabLlity increases. If
permeability of a clay soil increases enough for flow to become turbulent
at the hydraulic gradient utilized, subsequently obtained permaability
values may be invalid even for comparative purposes .
Laboratory permeability studies can be need to estimate permeability
in the field or to evaluate relative effects of different factors on perme-
ability of a clay liner. The former is by far more diffic’ilt to perform
due to difficulty in exactly dupifeating field conditionc. Comparative
permeability studies can be performed mre easily since rigorous
49
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duplication of field conditions are not essential so long as flow is
laminar and particle migration is minirtal.
Several authorities on perneahilicy studies have epressed doubts that
laboratory permeability tests are capable of reproducing field conditions.
Olson and Dar Ioi (1979) noted that the volume of soil sampies used in
laboratory tests are almost always too small to contain statistically
significant distributions of macrofeatures encountered in the field (i.e.,
sand lenses, fissures, joints, channels, root holes, etc.). They further
noted that samples taken in the field may be affected either b; collection
method or selection of the most unifornj or intact sample. Bowles (1978)
stated that “The soil in the permeability device is never in the same state
as in the field—it is always disturbed to some extent.” Zimmie et al.
(1981) stated that “It is virtually impossible to thiplicate field hydraulic
gradients in the laboratory. Test times become excessive and it becomes
difficult to obtain accurate cieasurements of flows and heads at very low
hydraulic gradients.••
Several factors not incorporated Into laboratory tests affect overall
permeability of clay. Sherard and Decker (1977) listed primary factors
determining “effective overall permeability” of a soil layer as being
continuity, regularity, thickness, and characteristics of interheded layers
or lenses. Laboratory permeability determinations on clay liners cannot
account for this type of variability and can only attempt to characterize a
nomogeneous sample o clay soil. Other factors that may lead to cliscrepan—
des between field and laboratory permeability values are discussed in
detail by Olson and Daniel (1979).
Comparative penneabilitv studies utilize multiple pernieameters to
isolate-effecta of one or more variables. This testing approach has been
widely used in agricultural irrigation studie evaluating the influeir’e of
various salt typea and concentrations on soils of low permeability
(McIntyre et a_., 1979; McNeal, 1974). Compzrative methods have also been
used to evaluate the influence of organic fluids on soils (t.lichaels and
Un, 1954; Van Schaik, 1970).
Permeability tests conducted for this study are strictly comparative
in nature and do not attempt to reproduce ypical field conditions. The
aIm of this study is to investigate the potential influet cc of various
organic fluids on permeability of compacted clay soils. Except where noted
In the dISCUSSiOn of test results, effects •)f factors other than soil—fluid
interactions are considered to be eliminated through establishnj n of base-
line perlneabilitjes for each sample usIng O.O IN Ca30 4 as initial pl rmeant
f laid.
Testing procedures used in this study are not suitable for exact
determinations of field permeability valuEs. They are, however, con3idered
suitable for performing rapid comparative studies to evaluate the potential
influence of waste fluids on permeability of compacted clay soil liners.
As there is a large variety of waste fluids placed in hazardous waste land-
fills and surface impoundments (Table 2), there is a great need for a
qualitative permeability test which can rapidly determine potential effects
50
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these fluids may exert on permeability of ciay lJr.eLs. As waste fluids
listed in Table 2 are but a fraction of fluid—hearing waste vpes disposed
In industrial landfills, rapid qualitative permeability tests that can be
perf ’rmed easily by laboratory technicians may be the only feasible method
for evaluating the impact of hazardous wastes on day liner integrity.
To simplify Jaboratory personnel trainIng and allow intercalibrat on
by independent laboratories, a qualitiative permeability test method should
use standardized procedures and readily a ailabie apparatli. The test
method developed for this study was designed with t iese objectives in mind.
n couparative permeability studies, flow should be laminar, and all
but the vat able being tested should be constant. Under these conditions,
any change in perma bility is the resu t of changes In the porous matrix.
Yong and Warkentin (97 ) noted that aside from independent fluid and soil
properties, permeability of a soil is affected by forces holding a fluid to
soil particles and soil—f iuld Interactions. They further noted that rela-
tive influence of any one factor on permeability was difficult to assess
since many are interdependent.
51
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SECTIOM 4
MATERIALS AND METHODS
To understand factors influencing permeability of clay liners to
organic fluids, it was necessary to construct a functional perspective.
This perspective includes the following components:
1. Delineation of physical classes of organic liquid—bearing hazard-
ous wastes.
2. Description of leachates generated by various waste classes.
3. Interpretation of fluid types contained by various waste Jeach—
ates.
4. Evaluatinn of characteristics of clay soils used to line disposal
facilities.
5. State—of—the—art review cf mechanisms invo’.xed in interaction
between organic fluids and clay soils that may alter peraeability
of clay Liners.
With this pec pective as a guide, representative organic fluids and
clay sells were selected, and merhodology was developed appropriate for
evaluati”g the influeoce of organic fluids on permeability of compacted
soils.
FLUIDS STUDIED
Seven organic fluids representing four classes of organic fluids and
water (Figure 5) were selected for use in comparative permeability
studies. Th four classes of organic fluld,, cLidied were acidic, basic,
- neutral polar, and neutral nonpolar. Table ii lists the seven organic
fluids and water along with their relevant physical and chemical proper-
ties.
Organic fluids used in this study were reagent grade (pure). Actual
waste leachates are normally a tnii ture of fluids combined with various
organic and inorganic solutes. In addition, waste leachates often contairt
particles in suspension that could clog or coat soil pores. While pure
organic fluids would not usually be discarjed, pure fluids were used in
52
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CIIEMTCAL PROPERTIES
Water
Solubil— Dipole
ity at Moment Molecular
20°C (debyes) WeIght
(g i/l)
TABlE 11. OSGANIC LUtDs ANt) WATER: RELF.VANT PHYSICAL AND
Temp. Range
of Fluid Density ‘/iscoslty Dielectric
FLUIDS State (°C) at; 20°C at 2O C Constant
Organic nj i iling (gm/cm 3 ) (Centipose) at 20°C
Fluid Name Point Point
Acid, Acetic
Carboxylic Acid
(Glacial)
Base, Aromatic
Amine Aniline
Neutral Polar,
Alcohol Methanol
Neutral Polar,
Ketone Acetone
Neutral
Polar, Ethylene
Glycol Glycol
Neutral Nonpolar,
Alkane Heptane
Neutral
Nonpolar, ylene
Alkyl—Benzene
Water
17
118
1.05
1.28
6.2
miscible
1.04
60.1
—6
184
1.02
4.40
6.9
34.0
1.55
93.1
--98
65
0.79
0.54
31.2
miscible
1.66
32.0
—95
56
0.79
0.33
21.4
miscible
2.74
58.1
13
198
1.11
21.0
38.7
miscible
2.28
62.1
—91
98
0.68
0.41
2.0
0.003
0.0
100.2
—47
139
0.87
0.81
2.4
0.20
0.40
106.2
0 100 0.98 1.0 80.4 1.83 18.0
-------
this study to elinLnate variables other than fluid propertie3 that could
affect the resulting permeabIlity values.
Glacial acetic acid was selected to represent the acidic organic fluid
class. Orgar i.z acids are b;’products of several lndus rial processes and of
anaerobic decomposition processes that occur in landfills. Aceti acid is
fluid at room temperature with a density and viscosity somewhat greater
than that of water. The dielectric constant is significantly lo. er, znd
dipole nomeni is only slightly lower than values exhibited by water.
Acetic acid is infinitely soluble in water.
Aniline is a slightly basic organic fluid at room temperature and
substantially soluble in wa r. 1: is considerably more vIscous and only
slightly more dense wa..er. As with acetic acid, aniline has a dielec-
tric constant ouch lower and dipole moment slightly lowe thafl values
exhibited by water.
Three neutral polar organic fluids studied are fluid at room tenpera—
ture and infinitely soluble in water. Values fo’: other properties decrease
in the following orders:
Density: Ethylene Glycol >Waer >Acetone Methanol
Viscosity: Ethylene Glycol >>Water >Acetone >Methanol
Dielectric Constant: Water >>Ethylene Glycol >t 1cthanoi >Acetone
Dipole Noinen.t: Acetone >Ethylene Glycol >Water >hethanol
Two neutral nonpolar organic fluids studie. are fluid at room tempera-
ture and \‘ery saringly soluble in .iter. Values for other properties of
these fluids de’:rease in the following orders:
Density: Water >Xylene >Heptane
VIscosity: Water >Xylene >}Ieptane
Dielectric Constans: Water >>Xylene >Heptane
Dipole >lonent: Wate: >>Xylene>Heptane
Water (O.OIN CaSO 4 ) was used as control fluid to establish baseline
permeability of each soil core. The calcium salt was selected due to its
stabilizing effect on permeability. Concentration of 0.O1N was selected
because it approximates salt concentrations typically found in soils.
CLAY SOILS STUDIED
Four native cLay soils with diverse mineralogical or chemical proper-
ties were selected for this study. Two of the soils had predominantly
smectitic clay minerals but different chemical properties. Two other soilr
contained predominantly kaolinitic and illitic clay minerals, respective-
ly. Additionally, ‘ ach soil was characterized by the following:
1. Exhibited permeability less than 1 x 10_i cm sec when compacted
at optimum water content.
54
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2. Had a geographic extent of at least. one million hectares.
3. Existed in deposits thick enough to pet&ait economic excavation
f r use as clay liners.
4. Contained a nininum of 35% (by weight) clay minerals.
Following collection, the clay solls were broken into golf ball size
clods and air dried. The soils were then ground sufficiently to pass
through an ASTM Number 4 sieve (4.75 mm) and stored at room temperatur? in
large drums prior to testing. Methods for determining scil pro etieu used
by Soil Physics Laboratories at Texas A& i Unive/sity ae described by Bla. k
(1965) except for moisture—density relations /ie:.e ASTM mettods were used.
General lnforr4atior. on the four soil/ is given in Table 12. This
includes soil series and order, its iocat1’ m geographically and within the
solum, and the parent material from which. ach soil was derived.
Table 13 gives grain size distribution of the soils and the mineralogy
of the clay sized fraction. Native clay deposits se dom contain only one
type of clay mineral, and these four clay soils are no excep ior.. The
mixed cation kaolinitic s’il conisins two predominant clay iineral species
(kaolinite and nalloysite). Clay sized quartz is present in all soils to
varying extents.
Physical properties of tie four clay soils are given in Table 14.
Properties determined for the toils in undisturbed states included shrink—
swell potential, pernieahfl!tv, cnlor, corrosivity, and structure. Other
properties determined on remr., .ded soil samples included lfquid limit
plasticity index, water retention, optimum notsture content, and nax num
dry density. Other values for physical properties of the remolded soils
can be found in Appendix B.
Chemical properties of the four soils are given in Table 15. The
distinctIon between noncalc3reous and calcareous snectites arises from
values for total alkalinities of 3.3 and 29.2 meq!lOOg respectively. The
calcareous nature of the latter is further illustrated by its content of
33% by weight calcium carbonate.
Other chemical properties of especially high potential for influencing
perneability include .he 3% organic matter content of the calcareous
smectite and the 13.2% Fe 2 0 3 content of the mixed cation illite. (The
kaolinitic and illitic clay soils we t e given the prefix “mixed cation”
because no specific cation predominates on their exchange sites).
Optimum water content for obtaininF maximum dry density of soil
subjected to a given compactive effort was determined for the four soils
using ASTM 698--b. Several compacted soil cores prepared for optImum water
content determinations were also utilized to determine th2 influence of
compaction water content on permeability of the soils to water (O.OIN
CaSQ 4 ). Figs. 11—18 show the resulting moisture—density—permeability
55
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TABLE 12. CE ERAL FROL’ERTIES OF TUE FOUR CLAY SOILS
Parent
Material
L u
Geographic
Setting
Slightly acid to
alkaline clayey
sediments.
Upland with 0—3%
sope.
Calcareous clays
and maria.
Upland with 0—8%
slope.
Old arine sediments
high in glauconite.
Upland with 0—157.
slope.
Calcareous silty
clay, glacial
U Li.
Lake plain with
0—2% slooe.
Extens (Ha)
>2.2 million
5.5 miLlion
>1.1 million
• $.3 million
General Location
East Central Texas
Blacklaud Prories
of Texas
Coastal Plains of
Texas
Northwestern
Ohio
Brazos County, Texos.
500 in south of FM 60,
1 km west of College
StatIon.
Bell County, Texas,
tr’jm intersection of
11S 190 a ’ 1 Texas 36,
go 1000 in southeast
on Tex 95, and go
800 in west northwest.
Wood County, Ohio,
on the grounds of
the Northwestern
Branch of Ohio
Agricultural Ron.
and Dcv. Center
—- — T) e ( ) 1 V jib .
(1) Soil Conservation Service (1976)
(2) gle. Ln and Wildjnt (1968).
-
—
-... ..- . ... ..
Clay Soil
Description
Noncalcareous( 1 )
Smectite
Caicareous( 1 )
Smectite
Mixed Cation( 1 )
Kaolinite
Mixed Cation( 2 )
illite
Soil Series
Lufk ln
Houston Black
Nacogdochcs
Hoytviile
Soil Order
Alfisol
Vertisol
Alfisci
Alfisol
Horizon
B2ltg
A 11 —A 12
B 2 lt L 2 t
B21g B22g
Location in
Solum (cm)
18—51
0—61
15—178
20—67
Type Locat1 n
Nacogdoches County,
Texas, from a road
Cut on the right
hand side of Hwy 105
goIng west, 20 kin
went of Nacogdoches.
-------
TABLE 13. GRAIN SIZE DISTRIBUTION OF THE FOUR CLAY SOILS AND
MINERALOGY OF THE CLAY SIZED FRACTIONS*
Clay Soil
Description
No
ncalcareous
Smectite
Calcareous
Smectite
Mixed Cation
Kaolinite
Mixed Cation
Illite
% Sand
(>50 am)
35—37
7—8
39—41
14—15
Z Silt
(50—2.0 urn)
26—28
42--44
17—18
38—39
% Clay
(<2.0 nm)
36—38
48—SO
42
7
Coarse Clay
( .O—O.2 nut)
Z of Total
16 (1)
25 (1)
33 (1)
61 (2)
Mineralogy
(3)
QZ—1
KK—2
MI—2
MT—i
KK—2
QZ—3
KK—1
QZ—2
I—i
QZ—2
Fine Clay
(<0.2 nu)
% of Total
84 (1)
75 (1)
67 (1)
39 (2)
Miceralogy
(3)
{r—1
cr—1
KK-3
iu —1
MI-3
I—i
MT-2
* All data from Soil Physics baboratories Texas 4 .&M University unless
otherwise noted.
(1) Soil Conservation Service (1976).
(2) Blevins and Wiiding (1958).
(3) Key to Mineralogy Data
MT = Smectlte 1 >40%
KK = Kaolinite 2 = 10—40%
I Illite 3 <10%
QZ Quartz
MI = Mica or Illite
Halloysite
57
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TASLE 14. PHYSICAL PROPERTIES OF THE FOUR CLAY S0ILS
Clay Soil. Noncalcareous Calcareous Mixed Cation Mixed Cation
Description Smectite Smectite Kaolinite Illite
Shrink—Sw ll
Potential “•ry high very high moderate aoderate
Permeabi Lity
(cmsec )** <4.5 x 1 ) <4.5 x 10 4.5 X 1O 4.5 x 10
Liquid !. iInit 51—67 898 41—60 4t, (1)
Plasti.ity Index 30—45 34—72 18—30 27 (1)
Color (dry) grayish brown very dark gray dark red gray (1)
Corro’;ivity
(steel) high high high N.D.
Water Retention
at 1/3 bar+ 31.0 (2) 48.0 (2) 21.0 (2) 30.0 (2)
Optimum Water
Content 20.0 (2) 21.5 (2) 20.0 (2) 19.0 (2)
Maximum Density
(kN m 3 ) 15.0 (2) 14.4 (2) 16.3 (2) 16.6 (2)
Structural Prismatic to blocky, Blocky, cricks Blocky, friable Moderate to
Description vertical cracks 1—10 cm wite when w en moist, hard strong, fine to
n ride. dry. when dry. medium angular
_______________ _____________ blocky.
All data from Soil Conservation Service (1976) unless oth rwi.;e noted.
(1) Blevins and Wilding (196P)
(2) Soil Physics Laboratories, Texas A&M University
N.D. Not Determined.
* Undisturbed State.
+ 7 by Weight.
% by Dry Wc Ight
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TABLE 15. CHEMICAL PROPERTIES OF THE FOUR CLAY SOILS*
Clay
Soil
Nortcalcare us
Calcareous
Mixed
Cation
Mixed Cation
Description
Sinectite
Smectite
Kaolinite
Illite
Cation Exchange
Capacity 24.2 36.8 8.6 18.3
(meqf 100 gin)
Exchangeable
Cations
(uieq/ 100 gin)
Na 1.4 1.4 0.1 0.1
K 0.3 1.0 0.2 0.4
Ca 18.5 51.8 (3) 1.3 17.3
Mg 6.3 I.E. 1.4 3.0
Water Soluble
Cations
(meq/ 100gm)
Na 0.49 0.84 0.33 0.62
K 0.22 0.27 0.12 1.86
Ca <0.01 0.25 0.02 0.03
Mg 0.04 0.06 <0.01 0.09
Total Alkalinity
(meq/100 gin) 3.3 129.2 0.8 4.2
pH (saturated
paste) 6.1 7.9 5.1 7.5
Ec (mmhos/cm) 0.2 0.4 <0.1 0.2
Fe 2 0 3 (ft) 0.42 (1) 0.2 (1) 13.2 (2)
Organic Matter (%) 0.9 (1) 3.0 (1) 0.6 (2)
CaCO 3 Equiv. (¼) 33 (2) Trace (2)
* All data from Soil Physics Laboratories, Texas A&M 1Jniver ity inless
otLerwise noted.
(1) Davidson and Page (1956).
.(2) Deren . inger (1968).
(3) Calcium value is high i’ie to dissolution of CaCO 3 by the extracting
solution used (l .ON Ajnmonium Acetate at a pH of 7).
59
-------
‘a
IT
16
‘5
‘4
13
z
>-
I—
0)
z
w
>_
0
FIG. 11. Conpactior. Moisture Content—Density Relationship for the
Noncalcareious Smectitic Clay Soil
I
10 IS 20 25
NONCALCAREOUS SMECTITE
/
/
/
— OPTIMUM
WATER
I CONTENT
60
-------
NONCALCAREOUS
SMECTITE
K5 5
x5 6
l()
w
(I )
E
C.)
—Jo
I-
-J
w
tu
I0
20
/
/
/
25
WATER CONTENT (% of DRY DENSITY)
FIG.12. Coinpactioi. Moisture Contet t—Permeabil1ty Pelatiunship for
the Noncalcareous Smectitic Clay Soil
x
61
-------
IT
‘3
‘E 14
z
>-
I-
CO
z
w
a
>-
a
I ’
(2 20 23 30
WATER CONTENT (% of DRY DENSITY)
FIG. 13. Compaction Moisture Content—Density Relationship for
the Calcareous Smectitic Clay Soil
G = 2.55
CALCAREOUS SMECTITE
OPTIMUM
WATER
\
\
(2
62
-------
CALCAREOUS
SMECT 1TE
12
K?
IS 20 23
WATER CONTENT (% of DRY DENSITY)
FIG. 14. Compaction Moisture Content -Permeabi1iZy Relationship for
the Calcareous Smec iti’ Clay Soil
63
‘ a 6
It,
6
>-
I—
-j
LU
cr -8
LU JO
0
x
— —
-------
‘a
IT
16
z
I5
>-
U)
z
w
>-
a
‘3
12
12 15 20 25 30
WATER CONTENT (% of DRY DENSITY)
FIG. 15. Compaction Xoistue Content—Density elationship
for the Mixed Cation Kaolinittc Clay Soil
G 2.75
MIXED C TtON KAOLINITE
OPTIMUM—
WATER
CONTENT
64
-------
WATER CONTENT
MIXED CATI” N KAOIJNITE
/
/
20 25
t% of DRY DENS TI)
FIG. 16. Cotnpact on Moisture Coritent—Perireability Relationah p
for the 4ixed Cation Kaolinitic Clay Soil
-4
I0
‘a 5
so
C l )
E
C-)
-J
4
w
U i
a-
1 7
,68
I2
x
‘C
30
65
-------
‘7
Is. OPTIMUM—A
WATE 1
CONTENT
‘5
‘4
In
7
>_
I-
0 )
7
w
>-
‘3
I?
12 IS 20 25 30
WATER CONTENT(% of DRY DENSITY)
FIG. 17. Compaction Moisture Content—Density Relationship
for the Mixed Cation Illitic Clay Soil
2.70
MIXED CATION ILUTE
-------
log
,6b0 —
I2
I
1
MIXED CATION ILUTE
- 20 25 30
WATER CON1 ENT (% of DRY DENSITY)
FIG. 18. Compaction I4oisture Content—Perueability Relationship
for the Mi,red Cation Illitic Ci y Soil
67
toe
‘C)
U)
E
C-)
‘a
I -
-J
U3
L j
cr
U i
0..
-------
relationships of the four clay soils. Data used in these figures is given
in Appendix A.
Percentage of soil voids filled with water after compaction at optimum
moisture content was approximately 757. and 907. for the two seectitic and
the other two clay soils resPectively. The minimum permeabi1 , value for
each clay was found to occur at or just above tha optimum moisture con-
tent. Particle densities (Gs) of the four clay soils are given on the
moisture—density graphs.
PERMEABILITY TEST CONSIDERATIONS, CALCULATIONS AND PROCEDIJKES
Tests on soils of low permeability must be ccrefully performed to be
accurate. Leaks, trapped air, vnlatile losscs, and turbulent flow or chan—
neling along the soil chamber wall can greatly affect permeability values
(Bowles, 1978). Each of these sources of error was considered in the
development of permeability test procedures. In additioa, steps were taken
to minimize inheren dangers associated with organic fluids under pressure.
Compacted claj soils often have permeability values ower than 1O cm
seC , and it may be necessary to pass a pore volume OL water through a
soil before a stable baselit’e permeability value it obtained. After estab—
lishing the permeability baseline, the passage of at least a pore volume of
organic test fluid may be necessary to fully determine effects the fluid
may have on permeability of the compacted clay soil. Consequently, a
pressurized air source hau been used to increase the hydraulic grddient and
reduce time needed for testing (Betine t, 1966; Jones, 1960).
Ath’.itionally, trapped air has been a common cause for artificially low
permeability values (Christiansen et al., 1946). Increasing the pressure
head exerted on a soil core reduces trapped air by ic’ reaslng the weight of
gas that will dissolve in water flowing through the core (jones, 1960).
Elevated pressure also reduces volume of remaining air pockets.
A pressurized aIr—induced, elevated hydraulic gradient was used in the
compatative permeability tests of the compacted clay soils. A hydraulic
gradient of 361.6 (equivalent to a hydraulic head of 42.2 m of B 2 0) was
used for the two sinectitic clay soils. A hydraulic gradient of 61.1
(equivalent to a hydraulic head of 7 m of lizO) was used for the illitic and
kaolinitic clay soils.
To avoid channel f .rmation, the compacLed clay soils were seated at a
hydraulic gradient of 1.85 (10 cm 1120). By letting 10 cm of standard
leachate stand on the soils for 48 hours, an effective seat was obtained
for the top few millimeters of soil. This thin layer prevented bulk flow,
thereby permitting the rest of the soil to adequately seal the permeaineter
sidewalls at elevated pressures.
68
-------
The form of Darcy’s Law used to calcuinte permeability is as follows
V
K =
iThere:
1< permeability constant (cm sec 1 )
V volume of liquid passed through the soil (cm 3 )
A = cross—sectional area of liquid flw (80.1 cm 2 )
h+l
H hyar.Aulic gradient
h hydraulic head (cm of H 2 0)
1 = length of soil (11.7 cm)
Permeability constants obtaIned with the above equation can be normal-
ized for liquids with various viscosities and densities by n ltip ying by
the density and dividing by the viscosity of the test fluid. By norcaiiz—
ing the impact of viscosity and density on permeabIlity, tt’e influence of
other factors on permeability changes can be observed.
Compacted soil cores used to evaluate permeability to organic fluids
were prepared at or above optimum water contcnt. Data on these cores are
prer ntcd it’. Appendix B. Itfter compaction, the roil cores were uounted on
permeameter base plates and fitted with fluid ehambers and permeameter top
plates (FIg. 1 ). Each top plate was fitted wit! a pressure intet connec-
ting it to a pressurized air source via the pressure distributim manifold
(Fig .20)
A moisture and debris trap, pressure regulator, and pressure gauge
were placed betceen the pressurized air source and manifold. The trap wa ;
positioned between the air source and regulator to ?revent Luildup of
debris on the regulator membrane. The pressurc gauge was placed between
the regulator and manifold so that the hydraulic gradient applied to the
permearneters could be monitored.
A pressure cutoff valve for each permeameter was placed between the
manifold and permeameter top plate. These valves allowed placement or
removal of individual permeameters vithout depressurizing other perneame—
ters.
All gaskets used in the permeameters were teflon to pr’ven t deteriora-
tion and possible blowout from contact with various organic fluids. To
avoid leakage around the hard teflon gaskets, all metal surfaces against
which the gaskets seated were wiped :lean .2 grIt. Permeaneter components
were found to withstand continuous operational use at pressures up to 60
psi (42.2m H 2 0).
69
-------
FIG. 19. Schematic of the Compaction Permeameter.
70
RELEASE
PERMEAMETER
TOP
BASE
I /U POROUS STONE
OUTLET—’ TEFLON TUBING
A
-------
VENTED HOOD
FIG. 20. SchematIc of the Compaction Permeaineter Test Apparatus
-------
Directly under the soil clinbers and in the permevaeter base plates
were poro ,s stones to permit seepage of effluent to the hace plate outlet.
To limit extent of effluent mixing after passage through the compacted
soils, the outlet was fitted with an adapter connected to 3 mm inside
diameter teflon tubing. The use of translucent teflon at the base plate
outlet provided a convenient window with which to monitor expulsion of
trapped air. Usually, at least one pore volume of standard leachate (0.OIN
C.aSO 4 ) had to be passed through soil cores before there were no air bubbles
vis hle in the outlet tubing. Where piping occurred in soil, cores, eluded
soil particles were visible both clingIng to the Liside walls of the outlet
tubing and as a suspension or precipitate in the effluent.
Teflon tubing carried the effluent to an automatic frar ’tion collector
which collected effluent samples simultaneously from ten permeameters at
specific time increments. Since there was potential for volatile losses
during effluent delivery front the tubing to the collection bottles, the top
of each bottle was fitted with a long stein funnel, and the fraction collec-
tor was placed in a refrigerated, air—tight chamber. Additionally, the
entire test apparatus was fitted into a vented hood (Fig. 20). This extra
precaution was taken as insurance against worker injury in the event of
accidental spills or s,stem leaks.
After seating the soils at low pressure, the selected air pressure was
applied to the permeameter fluid chamber until stable permeability values
were obtained with the standard leachate. At this point, pressure was
released and permeaneters disassembled to permit examination of the core
for signs of swelling or deterioration. If th soil had expanded out of
its mold, the excess was removed with a straIght edge while trying not to
smear the surface of the soil. The material that had expanded out of the
core was oven dried and weighed to estimate percent swelling that had taken
place.
With the three soil types that had swollen, additional standard leach—
ate was pas.ed to ensure that permeability was not affected by the excess
s ’ ii removal. This extra procedural step was not necessary with the
caolinitic soil since it underwent no swelling after passage of standard
leachate.
Next, the remaining standard leachate wi ’s removed and replaced with
the organic fluids for all but the contro.. pemmeameter. After passage of
between 0.5 and 2.0 pore volumes of simulated primary leachates (organic
fluids), the permeanieters were depressurized, disassembled, and the cores
dissected t determine if structural changes had occurred itt the compacted
clay soils.
For determining breakthrough urves, the percentage of organic fluid
in the effluent was determined by one of two methods depcndL’g on the fluid
analyzed. Immiscible fluids were determined simply by recording the volume
of each fluid layer in the sample collection bottles. The only miscible
fluid for which determinations were made was methanol. Percent methcaol Ic
water was determined usit g themmoconductivity gas chromatography.
72
-------
SECTION 5
RESULTS AND DISCUSSION
Permeability values for the clay soils were Diotted against cumulative
pore volume of test fluid that passed through the compacted core. Volume
of effluent was divided by volume of pore space in a given core to obtain
the fraction of a pore volume passed at each permeability value. The
vertical dashed line on each graph indicates the point at which standard
leachate (O.O1N CaSO 4 ) was replaced by organic flui’Js. For several soil
cores, breakthrough of organic fluids was plotted across the top of the
permeability graphs. All permeability data is given in Appendix C.
Following are discussions of effects seven organic fluids and water had on
permeability of four clay soils.
WATER (O.O1N CaSO 4 )
P rineability of four compacted clay soils to standard leachate (O.O1N
CaSO 4 ) are depicted in Fig. 21. Depressurization which occurred at the
dashed line appears to have had little effect on permeability. Noncalcar—
eous smectite and mixed cation kaolinite soil permeability values were
essentially constant during passage of approximately two pore volumes of
standard leachate. In contrast, permeability of calcareous smectite
decreased slowly while that of the mtxei cation illite increased slowly.
Both permeability chances were, however, relatively smal)..
Relative pert eabllity values for the four clay soils ta water are
consistent with values typical for those clay types (Fig. 7). Kaolinite
exhiolted the highest, noncalcareous (partially sodium saturated) smectite
showed the lowest, and calcareous (calcium saturated) smectite and mixed
cation illite had intermediate permeability.
After passage of two pore volumes f standard leachate, the four clay
soils exhibited no visible aggregations and appeared to have retained their
ir.itialiy massive structure. In dJition, the surface of the soils showed
no signs of large pore development (Fig. 22).
ilean and standard deviation of permeability to water (O.OIN CaSO 4 ) for
each soil type and individaa 1 soil column used in the study are listed in
Table 16. Variabilii.y in the permeability va].ues was small in all cases.
Permeability values of the mixed cation illitic soil exhibited the highest
degree of variability of the four clay soil types tested.
73
-------
a5
I
—
OLO
NOfiCALCAREOUS SMECTITE A
CALCAREOUS SMECTITE
MIXED CATION KAOLINITE 0
MIXED CATON ILUTE
0:5
PORE
WATER (o.o1r4 CaSO 4 )
I .
2.0 - 2.5
1.0
VOLUMES
FIG. 21. Permeability of the Four Clay Soils to Water (O.O1N CaSO 4 )
Since permeability of all soil columns were initially determ ed with
water (O.OIN CaSO 4 ), the columns were fully saturated prior to exposure t.o
the organic fluids. There are industrial landfills with conditions that
may maintain clay liners in an unsaturated state, such as landfills that
are in the drier climates prevalent in parts of the western and central
U.S. or that have an effective leachate removal system. However, ncst
WI ’ . ,.
E -
(a -
-
I-
-j
Lu
L i i
a-
a
A
I0
74
-------
FIG • 22. Suu1 ice of the Uónc , r trejt.is Sm et it i.e i: y SoJ.1 ;iFtt r Pn s; ’e
of Two Pore Vo1umc of 3ter (Q.O1N c. so 4 )
Lfl
a-
( 4
0
—
0
-------
TABLE 16: PERMEABILITY OF FOUR CLAY SOILS TO WATER (O.O1NCaSO 4 )*
Fluids to Which
the Soil Column
Would be
Exposed
-— ———4-
— PERMEABILITY (cm sec )
— — - -.
Noncalcareous Calcarcous Mixed Cation Mixed Cation
nectite Smectite Kaol.iflite Illite
—— —— — - — —
Water
(O.O1N CaSC 4 )
Acetic Acid
Aniline
Ethylene Clyc l
Acetone
Methanol
Xylene
Ueptaie
2.14(±O.26) x iO
1.59(±O.19) x 1O
2.91(±O.23) x iO-
1.39(±O.14) x
1.14(±O.lO) x
1.55(±O.17) x 1O
1.64(±O.21) x iO
l.51(±O.13) x 1U
7.77(±fl.G4) x 1O
6. (±O.11) x i0 9
3.86(±O.19) io 9
4.67(±O.64) x iO
3 .47(±C.6f,) x iO
5.O7 ±O.52) x 1O
5.62(±O.11) x 1O
3.62(±O.37) x
1.92(±O.18) X i0 8
I. o(±O.35) X i0 8
1.51(±O.12) x i 8
1.55(±O.35) 1O 8
2.O1(±O.12) X lO
1.46(±O.42) x
1.77(±O.15) x 1O
J.87(±O.iO) x in 8
6.07(±3.88) x iO
7.31(±O.93) , 1O
3.87(±1.62) x
6.75(±1.52) x 1O
3.06(±O.69) X iO
5.54(±1.52)
3.51(±1.13) x IO
4.26(±O.99) x itr 9
All Permeaneters
1.63(±O.5O) x 1O
4.98(±1.60) x iO
1.71(±O.25) x iO 8
514(±220) x
* Values for individual columns represent mean ± one std. dcv. of 2—7 permeability measurements.
Jalues given under the designation ‘All Permeameturs ” 1epresent mean ± one std. dcv. for all soil
columns of a given soJi type.
-J
0 ”
-------
industrial landfills are located in relatively wet climates such as the
Gulf Coast, Great Lakes, northeast and outheast regions of the U.s. (EPA
1980d, EPA 198de). These wctter climates would most probably maintain any
buried clay soil near saturation.
Traditionally, permeability tests. on prospective clay liners for
hazardous waste landfills and surface impoundments have used only standard
aqueous leachates (such as 0.OIN CaSO 4 or CaCI) as the permeant fluid. All
four of the clay soils used in this st d” if only e ’aluated by this tradi-
tional test, would qualify as adequate for lining hazardous waste disposal
facilities Ott the basis of their havir.g permeabilities lower than 1 x io—
cm sec 1 .
ORGANIC CIL’ — ACETIC ACID
Ali four clay soils permeated with acetic acid showed initial
decreases in perueability (Fig. 23). However, a si nificar .t amount of soil
piping occurred in these cores, indicated by soil particles clinging to the
inside walls of the outlet tubing and ‘eposited on the bottom of effluent
collection bottles. In addition, effluent from these cores was usually
tinted (red, cr .. amy, or blac. ) indicating that soil components were dis-
solved by the acid. Initial decreases in permeability are thought to be
due to partial dissolution and subsequent migration of soil psrticles.
These migrating particle fragments could lodge in the fluid conducting
pores, thus decreasing crcssectional are available for fluid flow.
Two of the soils treated with acetic acid (calcareous smectite and
mixed cation kaolinite) showed continuous permeability decreases throughout
the test period. After passage of approximately 20% of a pore volume, the
acid treated kaolinitic clay generated a dark red coloreo eff].uent that
smelled of acetic acid. The color was probably due to dissotuticn of iron
oxides which comprise about 137. of the solids in the kaolinitic clay
soils. The acid treated calcareous smectite began passing cream colored
foamy effluent after passage of about 2C7. of a pore volume. Since the solid
fraction of this clay soil is approximately 33% calcium carbonate, the
largest portion of the creamy material was probably dissolved calcium,
while the foam was the result of CO 2 liberation from the dissolved carbon-
ates.
Both noncalcareous smectite and the mixed cation illite eventually
showed permeability increases after the initial decreases, but the increase
did not begin until passage of 39% and 62% of a pore volume respectively.
Effluent from the noucalcareous smectitic clay contained soil particles and
a black ash—looking material, while effluent from the illitic soil con-
tained red tinted soil partii les that became increasingly darker as more
effluent was passed. Perneebllity increases with both of these soils were
probably due to progressive soil piping that eventually cicared initially
clogged pores.
77
-------
NONCALCAREOUS SMECTITE
CALCAREOUS SMECTITE £
MIXED CATION K LN TE 0
MIXED CATION ILLITE G
ACETIC ACID
-S
0
U)
E
U
I —
-J
LE
U i
Ui
0
PlC. 23. Permeability of the Four Clay Soils to Acetic Acid
In light of the across—the—board piping that occurred with the acid
treated clays, any fluid (such as strong acids and bases) capable of
dissolving clay liner components could potentially cause Increases in the
permeability of the liner. It would seem that neutralization of acids and
bases prior to their disposal would be the best safeguard against clay
liner failure in these cases.
Ui
(-)
z
to
PORE VOLUMES
I.
78
-------
The density to viscosity ratio of acetic acid (0.82) infers that
permeability should decrease approximately 18% from the value obtained with
standard leachate. However, the large permeability decreases and subse-
quent increases (in two of the soils) indicate that soil piping was the
predominant influence responsible for permeability changes.
ORGANIC BASE — ANILINE
permeabilities and breakthrough curves for the four clay soils treated
with aniline are given in Fig. 24. While all four clay soils showed
significant permeability increases, calcareous smectite showed the least.
Both noncalcareous smectite and mixed cation illite had breakthrough
of aniline with concurrent permeability increares at lower pore volume
values (<0.5) than the other two clay soils. There was some indication
that the permeability of the noncalcareous smectite was reach ng a constant
value just above 1 x i0 7 cm sec .
Permeability climbed above 1 x iO cm sec and aniline broke througn
after passege of one pore volume for the kaolinitic soil. Only the calcar--
eous smectte clay maintained a permeability value below I x o— cm
sec 4 . Its permeability increased rapidly at first, but showed substantial
decrease concurrent with aniline breakthrough. After the permeability
decrease, this soil exhibited a slow hut steady ermeability increase.
There were no signs of migrating soil particles in any effluent
samples collected from the four aniline treated cores. Apparently, aniline
is too weak a base to cause significant dissolution of clay soil compon-
ents. However, examination of the cores subsequent to the permeahility
tests indicated that the organic base caused extensice structural cha iges
in tha upper half of the soil cores. The massive structure of the four
soils after treatment with standard eachate was altered by aniline into an
aggregated structure characterized by visible pores and crackF in the
surface of the soils [ Fig. 25(upper left)1. Fig. 25(upper right) shows
aggregated soil removed from the surface of the noncalc.areouS ,nectitic
clay soil. Fig. 25(lower two) details the platy soil structure exposed by
excavation of the soil surface.
According to the equation for intrinsic permeability, a permeant fluid
with density and viscosity of aniline should result in soii permeability
77% lower than that obtained with water. However, the four soils tested
underwent permeability increases of between 100% and 200% when permeated
with aniline. It appears that the predominant factor affecting permeabil-
ity was the ability of aniline to alter the structural arrangement of
particles making up clay soils.
79
-------
NONCALCS REOUS SMECT 1TE
£
0
.
£
—‘a
ANILINE
FIG. 24. Pcr eability and Breakthrough Curves of
the Four Clay Soils Treated with Aniline
3.0
I—
LLJZ
zw
—i--I
— I L.
ZLL.
-s
C)
1)
U
5
I-
-j
w
U i
a-
Ui
z
CALCAREOUS SMECTITE
MIXED CATION KAOLINITE
MIXED CATION ILUTE
0
N
A
A
1.0
PORE VOLUMES
80
-------
FIG. 25. urfacc (upper left), Rwnoved Soil (iipp ’ r right), ; tid the Soi.t Expo3ed after Core
Exc.i it1on (low’r Iwo) of the AriiiIne Treated • oncalcareous Smectitic Clay Soil
-------
NEUTRAL POlAR ORGANICS
!ilene Glycol
Permeabilities of the four clay soils to ethylene glycol are depicted
in Fir;. 26. As withaniline—treated cores, permeability trends with ethyl-
ene glvcol showed little consistency with predicted intrinsic permeability
values. The ratio of denrity to viscosity of ethylene glyco! suggests that
resulting soil permeability should be only 5% of that obtained with water.
However, actual permeability values indicated that it was the ability of
ethylene glycol to alter the soil fabric that waa the dominating influence
on permeability.
Three of the clay soils treated with ethylene glycol showed initial
permeability decreases. The kaolinitic clay soil continued to undergo
7 ermeability decreases as long as It was ! eing tested. The illitic clay
soil began showing a permeability increase after passage of 0.5 pore
volumes. In contrast, the calcareous smectite followed its initial permea-
bility decrease with a substantial increase, a second decrease, and finally
reached a nearly constant value that contin ied until the end of the test
period. Noi e of the three clays that showed Initial permeability decreases
ever reached permeabilities greater than I x 10 cm sec’.
The noncalcareous smectitic clay soil treated with ethylene glycol
showed an initial rapid increase in permeability and a slower but continu-
ous Inclease after passage of 0.5 pore volume. Its permeability exceeded
I x 10’ cm sec’ after passage of two pore volumes.
Permeability trends in ethylene glycol treated cores emphasized the
need to pass at least one pore volume of an organIc leachate to determine
if the fluid is likely to affect permeability of a prospective clay liner.
In addition, if the permeability Increases during the passage of the first
pore volume, an additional pore volume shuuld be passed through the core to
determine tl’e upper limit of the permeability increase.
Ace t 0112
permeabilities of the four clay soils to acetone are given In Fir.
27. Three of the acetone—treated soils reached permeabilities in excess f
1 z 10 cm sec 1 prior to tne passage of one pore volume, while the cal—
careous sniectitic soil exceeded this permeability within 1.5 pore volumes.
While density to viscosity ratio of acetonc (2.4) IndIcates that
pert!.aability should Increase 240% over values obtained w.th water. the
observed permeability increases actually exceeded 1000% for the acetone—
treated soils. The illitic and calcareo*_ smectitic clay soils underwent
100 fold (10,000%) permeability increases, while tb noncalcareous smecti—
tic clay soil had a 1,000 fold increase.
82
-------
CALCAREOUS
SMEC11TE
3.0
PORE VOUJMES
FIG. 26. Per ab lity of the Four Clay Soils to E ylene Glycol
It is interesting to note that all soIls treated with acetone had
initial permeability decreases. These decrcases continued until passage of
approximately 0.5 pore volume. During passage of the next 0.5 pore volume,
however, the soils underwent large permeability ir.creases. One possible
explanation for this sequence of permeability changes s as follows:
1. The higher dipole moment of acetone caused Initial increase in
interlayer spacing between adjacent clay particles as compared to
water only.
w
z—J
L&jo
-Jo
>->.
x-J
‘—0
w
0
I-
0
5&
U
C,
0
E
U
>-
I-
-J
In
IzJ
L i i
a-
NONCALCAF EOUS SMECTITE
MIXED CATION KAOL 1N1TE
£
MIXED CATION ILUTE
0
ETHYLENE GLYCOL
83
-------
2. As more acetcne passed thrcugl the soil cores, more water i yers
were removed from clay surfaoes. Due to it3 larger molecular
weight, i owev i-, fewer acetone layers were adsorbed than ad
adsorbed when water was the only fluid pre3ent. This resulted in
a larger e ct1ve croas—soctooal area ava leble for fluid flow.
While acetone can displace water from clay surfaces due to its hIgher
dipole moment, it cannot form as ma!L’; adsorbed fluid layers as water due to
its higher molecular weIght.
cALCA1 EOU& SMECTITE
MIXED CATION KAOLINITE
MiXED CATION ILUTE
ACE1ONE c )L .cH 3
2.0
FIG. 27. Permeability of the Four Clay Soils to Acetone
U
4)
E
U
>.
I-
U i
(LI
a-
NONCALCAREOUS SMECTITE
£
0
0.5
S
0.5 1.5
PORE VOLUMES
84
-------
In a previous study conducted by Green et al. (1981), this sace
initial decrease in permeability occurred with three other acetone—treated
clay soils. Apparently, however, the tests were not of sufficient duration
to pass enough af a pore volune to observe the large permeability increases
as occurred in the present study above 0.5 pore volumes. This iurther
illustrates the importance of passing at least one full pore volume of a
waste 1 machate to determine tiow the fluid will affe t the permeability of a
clay liner.
Examination of the soil after acetene reatment showed extensive
shrinkage and cracking. Such soil slmrThkage usually associated
with dehydration, indicating that acetone had e’ Li.cted water from soil
particle surfaces.
Nethamol
Permeabilitjes of the four soils treated with methanol and a break-
through curve for the illitic clay soil are given in Fig. 23. As with
acetone—treated roil cores,, soil permeated with methanol reached permeabil—
ities greater than 1 x 10 cm sec’. t nlike soils treated with acetone,
methanol—treated soils underwent no initial per -meability decrease.
Percent methanol in the effluent from the illitic clay soil paralleled
an increase in permeability of the soil. After passage of :.5 pore
volumes, the h dr -:lic gradient was reduced from 6].1 to 1.85 cad another
pore volume of methanol passed (Fig. 29). Afer at. initial decrease, perme-
ability of the soil steadily increased at the lower hydraulic gradient to a
value greater than I x 10_s cm sec .
No particle migration was detected in effluent from methanol—treated
cores, and therefore soil pi ing was discounted as a mechanism for observed
permeability increases. If these ircreases were due solely to the 1.46
density to viscosity ratio, permeability of the cores would have leveled at
values 150% of those obtained with water. Instead, the cores showed steady
permeability increases to values greater than 1,O00 (kaolinitic soil) and
io,ooo% (illitic and noncalcareous soils) of permeability values with
wa t e r.
Examination of methanol—treated soil cores revealed development of
larg€ pores and cracks virible on the soil surface (Fig. 30). The lower
dielectric constant of methanol may have caused a decrease in interlayer
spacing of the clay minerals preseut in the soils and thereby promoted the
structural changes. Table 8 shows the trend relating dielectric constant
to Interlayer rpaaing tor pro mnol, another low molecular weight alcohol,
in “erious concentrations of water. In the case of propanol treated clay,
it can be seen that both the dielectric constant of the fluid and the
ir .terlnyer spacing of the clay decreaseL as the percentage propanol in the
fluid increased.
85
-------
CALCAREOUS
SM ECTITE
FIG. 28. Permeability of the Four Clay Soils to Methanol and
the Breakthrough Curve for the Methanol—Treated
Mixed Cation Illitic Clay Soil
oz
ZW
I-i
La
0
4-
w
U)
E
C)
>-
-J
03
I ii
cr
hi
a-
0
c.J
=
0
a:
Li
hi
z
=
0
NONCALCAREOUS
SMECTITE
MIXED CATION KAOLINITE
£
MIXED CATION ILUTE
0
0
METHANOL
CH 3 OH
O 5
PORE VOLUMES
‘5
86
-------
()
4,
E
>-
I-
-j
l ii
a-
FIG. 29. Permeability of the Methanol—Treated Mixed Cation Illitic
Clay Soil at Two Hydraulic Gra’ ients
NEUTRAL NONPOLAR ORGANCS
pcrmeabi.lities and brcakthro’ gh curves of the four clay soils reared
with xyl ne are given in Fig. 1. Xylene—treated soils showed rapid
I0•
H:61.1
H 1.85
METHANOL. CH OH
0.5
PORE
‘5
VOLUMES
Xyler e
87
-------
fJ_
a.
—m
( O
1,
0,
FIG. 10. Surface of the Methanol—Treated Noncalcareous Sr titLe Clay Soil
-------
NONC! .LCAREOUS SMECTITE
ALCAREOUS SMECTITE
MIXED CATION KACLIMTE 0
MIXE [ ) CATION ILUTE
XYLENE
0.5 0.0 O 1.0 1.5
PORE VOLUMES
2.0
2.5
FIG. 31. Permeability a d Breaktr rough Curves of the Four
Clay Soils Treated with Xylene
3
LLJ
zw
>-IJ
XL&.
U
c i )
U)
E
C-,
>-
I —
-J
co
Li
a::
LI
0
II
3.0
89
-------
permeability increrses followed by nearly constant permea ilities roughly
two orders of magnitude greater than their permeabilities to vater.
Permeability increases due t the ratio of density to viscosity of
xylene (1.07) accounts for only a 7X incr ase ir. permeability over valuc-s
obtMned wiLh water. Since permeability incroases averaged 10,000% (two
orders of magnitude), othe nechanisms are o w .. .ously iI.vol?ed. An indica-
tion of these mechanisms vas the structural changes in the xylene—treated
soils, exemplIfied by massive structure before treatment and blocky struc-
ture after the soils were treated with xv]ene.
An earlier study by Green et al. (1981) noted that neutral nonpolar
compounds such as xylcne may greatiy increase permeability of compacted
clay soils by causing the formation of shrinkage cracks. This study how-
ever, erroneously listed the “equilibrium coefficient of permeability” for
the xylene—treated soils as the low permeability values obtained prior tc’
the formation of the shrinkige cracks. The authors compounded this error
by plotting the artificially low permeability values for these neuti l non-
polar fluids versus dielectric constant and arrived at the following
conclusion: “All clay soils were mo :e pcrmeabl to at r than to organic
solv nts. ”
Rent are
Permeabilities and breakthrough ct’rves of the four clay soils treoted
with heptane are given in Fig. 32. Prereability pntterns fuc the heptanc-
cores closely approximated those shown by the xylene treated cores. That
is, the cores underwent initial permeability increaces of roughly fl,000%.
Following these init-ial large increases, rate of pern’eability increase
slowed until nearly co’ stant permeability values were observed.
Only thu calcareous sme titic clay showed a significant differenca ir
its permeability to the two neutral nonpolar liquids, with its permeability
to 1eptane well below its per. ieability to xylenu.
The constant permeability vaiues eventually reached by the neutral
nonpoler treated cores were rob. -bly related to the limtted ability o
these f .uid to penetrate inter)ayer spaces of the clay minerals. Permea-
bility trends for nentral nonpolar fluids differed from the continucus
permeability increases observed In clay soils treated with neutral polar
fluids, acetone and methanol.
REINTRODUCTION OF WATER
As stated earlier, changes ir. permeability for clay so!ls treated with
organic fluids do not follow trecds that would be predicted simply from
changes in viscosity and density of thn permeant fluid. Fig. 33 gives the
permeability and breakthrough history of the noncalcareous smerticir clay
90
-------
2.0
j IC. 32. Ptrmeability and Breakthrough Curve3 of the
Clay Soils Treated with Heptane
Ui ’—
Li-
w Li
I{Li
IO
0
F-
0
-I-
-a-
-S
U
U,
E
U
I-
-j
a)
tii
Ui
a-
NONCALCAREOUS SMECTITE
CALCAREOUS MECT!TE
MIXED CATION KAOLIMTE
MIXED CATICN ILLITE
£
0
ci
0.5
0.0
HEPTANE
0.5 1.0 15
PORE VOLUMES
2.5
.0
91
-------
w
z
-J
z
0
I-
0
C,’
=
0
a:
LL
L i
z
=
C-)
A
PORE VOLUMES
FEC. 33. Parmeability and Breakthrough Curve for the Noncalcareous
S ctitic Clay Soil Tr€ated Sequentially with Water (O.O1N
CaSOj ,), Aniline, and Water (O.O1N CaSO 4 )
t00•
0
WZ
zw
ZLL.
-
I—
-J
0
Li
cr
Lii
0
0:5
ANtLINE
‘.5
92
-------
soil sequentially permeated with water (O.O1N CaSO 4 ), aniline, and water
(O.O1N CaS0 4 ).
According to intrinsic oermeability theory, more viscous aniline
shoulL render the soil lecs permeable than water. I fact, the opposite
trend w s obserwed. Aniline increased permeability nearly two orders of
magnitude. Reintroduction of water caused a subsequent decrease in the
permeability of roughly one order of magnitude. Since reintroducth,n of
water did not return the soil to its odginal permeability to water, there
was at least partIally irreversible structural alterations caused by the
interaction of aniline with the compacted clay soil.
Water was also reintroduced on the noncalcareous suectitic clay soil
after the sol’ h id been treatec with methanol and ethyiene glycol (Table
17). Tht permeability trend (observed when water was reintroduced on the
aniline—treat. d soil) also held f r both the methanol and ethylene glycol—
treated soils.
USE OF ELEVATED HYDRAULiC CRADTE TS
Two ele’;ated gradients were used to short ii the tine rcquired for
these permeability studies. A gradient of 361.’ s used with the smecti—
tic clay soils and a gradient of 61.1 was used with both the illitic and
kaolinitic clay soils. There were no signs of partic 1 e migration or turbu-
lent flow in the neutral or basic organic fluid treated clay sails at
either gradient. In edditlon, the gradients ,i.sc did not appear to affect
the permeability trend . .bli’; ied by water or the organic fluids.
A disadvantage of using the higher gradient (361.6) was the r 3uidity
with which permeability changes occurred. On several occasio is, an
TABLE 7: PE! MdABILITY OF NONCALCAI EOUS SMECTITIC CLAY 3OJL
TO THE FOLLcJWING FLUID ,EQ1JENCE WATER (C.O1N CaSO )—
TCST FLUID—WATER (O.OIN cnso 4 )
Test
Fluid
Initial Permeability
to Water (O.OIN CaSO 4 )
(cm sec )
rmeability
to lest Fluid
(cir sec )
Final Permeability —
to Water (O.OIN CaSO 4 )
(cm sec )
Aniline
2.91(±O.23) x
2.2 x iO
2.3 x i c r 8
Methanol
1.55(±O.17) x iO
1.1 x o—6
6.0 x icr 8
Ethylene
Glycol 1.39(±O.14) x icr 9 3.1 i@— 1.1
93
-------
increase occurred so quickly that the entire fluid reservoir was depleted
before the end of a sampling period, thus permitting air to blow through
and denydrate the sail.
There were two main advantages of using the low hydraulic gradient
(€1.1). First, the lower gradient retained the advantage of a si ortened
testing time. Secondly, perr eabtlity changes at the lower gr:ulient
)ccurred slowly enough to obtiirt several points along a changing
permeability curve.
94
-------
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106
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APPENDIX A
MoIDTuRE-DENSrrY—pE1 MEABIL1TY RELATIONS DATA
TABLE A—I. MOISTI E DENSITY—PF,RN ABILI Y RELATIONS OF
NONCALC REOUS SM CTLTE SOIL
Water Content Dry Density Permeability
(% of Dry Density) (kNm 3 ) (cm sec 1 )
14.1
11.7
1.55
x iO
16.6
14.2
2.51
x 1O
17.8
14.8
ND
20.0
15.0
1.50
x 1Q
21.7
14.7
2.54
x iO
21.8
14.6
ND
..._••_•_
ND — not determined.
107
-------
TABLE A—2. M0tST RE—DENSITY—PE RNEABIL1TY RELATIONS OE
CALCAREOUS S 1ECTtTE SOIL
Wat
(% of
er Content
Dry Density)
- Dry Density
(kNt 3 )
Perme
(cm
ability
e 1 )
15.9
12.)
7.00
x
16.4
12.6
ND
18.0
13.3
1.75
x 10
20.0
13.5
2.13
x 10
20.7
14.5
ND
22.1
14.4
6.13
x 10’
22.6
14.4
ND
23.3
13.7
5.24
x io
23.5
14.1
4.49
x 10
ND — not determined.
108
-------
TABLE A—3. MOISTIJRF DEN ITY-PERMEA ILITY RELATIONS OF
MIXED CATION OF KAOLINITE SOIL
Water Content Dry Density Pern eabI1ity
(% of Dry DensitY) (k n ) (cm ‘ec 1 )
16.2 15.7 6.23 ; 1O
18.8 16.4 4.39 x JC 8
21.7 16.0 1.78 x i08
21.7 16.2 1.98 x iO
22.0 16.1 1.32 x 1O
22.3 13.7 2.06 x io8
23.9 1i.4 1.70 x 1O
24.6 15.2 2.61 x
1e9
-------
TABLE A—4. MOISTURE—DENSITY--PERMEABILITY RELAT10 S OF
1 LITE SOIL
Water Content Dry Density Pert eabi1ity
(% of Dry Density) ‘ kNm 3 ) (cr sec )
15.6 16.4 8.83 x
17.3 16.5 5.23 x
19.0 16.6 6.94 x 1O
20.2 16.5 5.03 x 10
22.1 16.5 ND
24.7 15.6 3.55 x
25.2 1 .4 3.49 x 10
26.5 15.1 4.83 x io 9
ND — not deter in d.
110
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APPENDIX B
PHYSICAL DATA ON THE SOIL COLUMNS USED IN THE STUDY
TABLE B—i. DATA ON THE NONCALCAREOUS SMECTITE SOIL COLUMNS PREPARED FOR THE PEP .XEAHTLITY STUDIES
(%
Compaction
Water
Content
dry density)
Dry Density
Before
Swelling
(kNm ’)
Dry D’ nsity
After
Swelling
(kNn( 3 )
%
Swelling
Porosity
After
Swelling
Pore Volume
After
Swelling
(cm )
21.7
14.7
14 .’
4
0.444
41
20.3
15.0
14.4
4
0.432
405
20.0
14.9
14.3
4
0.437
409
20.0
14.8
14.4
3
0.434
407
21.5
14.6
14.0
0.448
419
21.5
15.3
14.6
5
0.626
399
21.5
15.1
14.5
4
0.428
401
21.7
14.8
14.2
4
0.439
411
-------
TABLE B—2. DATA ON rHE CALCAREOUS StIECrICE SOIL COLJMNS PREPARED FOR THE PERMEABILITY STUDIES
Ccu ipaction
bry Denoity
Dry Density
Porosity
Pore Vo.u.’ne
Water
Before
After
7.
After
. .fter
Content
(7. dry densIty)
S e11.tng
(k 14n 3 )
S e11ing
(kN i )
SweUing
Swelling
Sw ]. rg
(cmi)
23.3 13.5 12.5 7 0.502 471
23.5 14.0 13.2 6 0.473 443
23.3 13.6 6 0.488 457
23.3 14.1 13.0 8 0.478 448
23.3 13.7 12.7 7 C;.493 462
23.5 14.0 12.9 8 U.4 6 455
23.5 14.0 12.9 8 0.485 454
23.3 13.3 12.3 8 0.510 478
-------
TABLE B—3. DATA ON THE MIXED CATLOt ! KAOLINITE SOIL COLUNNS PREPARE!) OR THE PERMEABILtTY STUDIES
Compaction Dry Density Dry Dcn’dty 1’oros .ty Pore Volume
Water Before After After After
Content Swelling Swelling Swelling Swelling Swelling
(% dry density) (kNia 3 ) (kNm 3 ) (cm 3 )
22.3 15.7 15.7 0 0.418 395
21.7 16.1 16. 1 0 0.400 373
21.7 16.0 16.0 0 0.407 385
22.0 16.1 16.1 0 ).4O4 381
22.2 15.7 15.7 0 0.418 395
22.3 15..i 15.3 0 0.433 409
2.1.7 15.7 15.7 0 0.418 395
22.1 15.4 15.4 1) 0.429 405
-------
TABLE B—4. DATA ON THE MIX O CATION ILLITE SOIL COLUMNS PREPARED FOR THE PERMEABtL TY STUDIES
Compaction Dry Density Dry De; ity Porosity Pore Volume
Water Refore After After After
Content Swelling Swelling Swelling Swelling Swelling
(% dry ‘lensity) (kNm 3 ) (kNm ) (cm 3 )
25.1 15.6 15.2 2.5 0.425 398
26.5 15.1 14.8 2.1 0.441 413
25.2 1! .4 15.0 2.5 0.432 405
25.6 15.4 15.0 2.3 0.432 405
26.9 15.4 15.1 2.0 0.430 402
24.7 15.6 15.2 2.6 0.426 339
25.4 15.6 15.0 2.4 0.435 408
24.8 15.5 15.1 2.6 0.431 404
-------
APPENDIX C
PERMEABILITY DATA ON THE SOIL COLUM1 S USED I T} E STUDY
TABLE C—i. PER ABILITY HISTORY FOIt THE NONCALCAREOUS SMET 1TIC CLAY
SOIL PERMEATED WITH H 2 0 (o.1N Ca50 4 ) ( CONTROL)
(PORE VOLUME 416 C 3 }111)RAULIC CRADIENT = 361.6)
K
T
Volume
Pore
(cm sec 1 )
(see)
(mIs)
Volume
2.15 x io 6.912 x 1O 43.0 0.51
.97 x iO 6. )i2 x 10 39.5 0.41
1.8’) x icr 9 6.912 x 1O 36.0 0.32
2.40 x io— .912 x 1O 48.0 0.23
2.37 x iO 6.912 x 10 47.5 0.11
“Fluid in” continue.1 wIth 1-1,0 (‘:‘.OJN CaSO 4 ) 0.0
h97 x 1O 6.912 x 10 39.5 0.09
2.00 x icr 9 6.912 x 10 60.0 0.19
2.00 x 1O 6.912 x 1O 0 .0 0.29
2.42 x iü — 9 6.912 x 1O 48.5 0.40
2.35 Icr 9 6.912 x 10 67.0 0.52
2.50 x i c r 9 6.q 1 2 x 1O O.0 0.64
2.32 x 10’ 6.912 x 10 46.5 0.75
2.50 x icr 9 6.912 x 1O 50.0 O.C7
2.52 x icr 9 6.912 x 10 50.5 0.99
2.55 x io 6.912 x 1O 51.0 1.11
2.45 x 1O 6.912 x 10 49.0 1.23
2.62 x io— 6.912 x 1u 5 52.5 1.36
2.45 x 1O 6.912 x 10 49.0 1.47
_.• _. • .
115
-------
TABLE C—2.
PERMEABILITY IISTORY FOR TUE NONCALCARECUS S 1ETLTtC CLAY
SOIL PNRMCATED WITH h 2 0 (0.Q IN CaSO 4 ) FOLLOWED BY ACETIC
AC 11)
(PORE VOL1 NE = 407 c m 3 ; HYDRAULIC GRADIENT 361.6)
K
T
Volume
Pore
(c m s’e )
(see)
(mis)
Volume
1.65 x
io
6.912 x 10
33.0
0.47
1.92 x
1o 9
6.912 x 1Q
38.5
0.39
1.65 x
io—
6.912 x
33.0
0.29
1.45 x
10
6.912 x 10
29.0
0.21
1.52 x
i —
6.912 x
30.5
0.14
1.37 x
io—
6.912 x J5
27.5
0.07
Fluid
In” changed
from H 2 O (0 .OIN
CaSO 4 )
to
Acetic Acid
0.0
1./S x
iO
6.912 x
35.0
0.09
1.37
io—
6.9i2 x 10’
27.5
0.15
1.02 x
io—
6.912 x 1O
20.5
0.20
6.50 x
1010
6.912 x
13.0
0.24
4.75 x
10—10
1.382 x 1O
19.0
0.28
x
lO
1.382 x io6
15.5
0.32
4.62 x
10—10
1.382 x 106
18.5
0.37
4.25 x
1.3.32 x io6
17.0
0.41
2.62 x
10—10
1.382 x 106
13.5
0.43
1.96
io-
1.382 x io6
78.5
0.63
2.77 x
1.382 x
111.0
0.90
6.26 x
io
1.382 x 1o6
250.5
1.51
9.85
lO
1.037 x 106
296.0
2.Z4
116
-------
TABLE C—3. PERMEABILITY hISTORY FOR THE NONCALCAREOUS S 4ETITIC CLAY
SOIL PERMEATED WITH ‘20 (O.O1N CaSO 4 ) FOLLOWED BY ANILINE
(PORE VOLUME = 419 Cm 3 ; HYDRAULIC GRADIENT 31.6)
Effluent K
H20(%) i\niline(%) (cm s0c’)
I
(sec)
Volume
(mis)
Pore
Volume
100 0 3.00 x 1O 6.912 x i0 60.0 0.55
100 0 2.95 x 1O 6.912 x 1O 59.0 0. 1
100 0 3.10 x 1O 6.912 x 10 62.0 O.U
100 0 2.57 x 6.912 x 10 51.5 0.12
“Fluid In” changec’ from 1120 (O.O IN Ca80 4 ) to A i1ine 0.0
100 0 2.52 x 6.912 x 10 50.5 0.12
87 ‘\ 13 3.00 x 8.64 x 7.5 0.14
19 81 3.41 x i08 4.50 x io 44.5 0.24
16 84 6.64 x i08 1.17 x io 22.5 0.30
1O “p90 8.94 x iø8 1.158 x io 30.0 0.37
<10 >90 2.28 x io 1.135 x io 75.0 0.55
Trace 10O 2.17 x io 1.638 x IO 103.0 0.79
Water (O.O1N CaSO 4 ) reintroduced as the “Fluid In” (0.0)
Trace 10O 1.60 x iO8 8.64 x 40.0 0.89(0.10)
4.22 x 10 8.64 x io 105.5 ..14(O.35)
3 20 x 8.64 x 80.0 1.33(0.54)
. 100 Trace 1.56 i 08 8.64 x 1O 4 39.0 1.43(0.63)
‘ 1O0 Trace 1.96 x io8 8.64 x 3O 49.0 1.54(0.75)
96 2.50 x i08 8.64 x IO 62.5 1.69(0.90)
‘1OO Trace 2.40 x iø8 8.64 x 60.0 1.84(1.04)
“10O Trace 2.28 x 1O 8.64 iO 57.0 1.97(1.18)
117
-------
TABLE C—4. PERMEABILITY -1ISTOi Y FOR THE NONCALCAREOUS SMETLTIC CLAY
SOIL PERMEAT1 WITH H 2 O (O.O1N CaSO 4 ) FOLLOWED BY ETHYLENE
GLYCOL
(PORE VOLUME 4i cm 3 ; HYDRAULIC GRADIENT 361.6)
K
T
Volume
Pore
(cm sec 1 )
(sec)
(mis)
Volume
1.42 x i0 1.382 x 106 57.0 0.54
1.22 x 6.°12 x 24.5. 0.41
1.40 x 1O 6.912 x 1O 28.0 0.35
1.50 x 10 6.912 x 10 30.0 0.28
1.52 x io— 6.912 x 10 30.5 0.20
1.52 x 10 6.912 x l0 30.5 0.13
1.17 x 1O b.912 x 23.5 0.06
“Fluid In” changed from 1120 (O.0N CaSO 4 ) to Ethylene C.lycol 0.0
1.40 x io 6.912 x 10 28 ) C,. 07
1.20 x i c r 9 : .456 io 12.0 0.10
4.00 x icr 9 8.64 io O.O 0.12
7.59 x 8.64 x io 19.0 0.17
8.79 x 1o 8.64 x io 22.0 0.22
2.08 x i0 8.64 x io 52.0 0.35
5.51 x ic r 8 8.64 io 138.0 0.68
6.87 icr 8 .64 x io 172.0 1.10
1.68 x 1u 7 8.64 x 420.0 2.12
1.80 x 10 4.dO x iO 25.0 2.18
2.24 x icr 7 3.84 x io 25.0 2.24
2.15 x i0 3.54 x i0 3 22.0 2.29
(Continued)
118
-------
TABLE C—4. CONTINUED
(c m
K
sec 1 )
T
(sec)
Volume
(mis)
Pore
Volu e
2.40
x
i08
1.32 x iO
9.0
2.32
3.07
x
10
3.60 x 1O
32.0
2.40
2.92
x
io
3.30 x IO
28.0
2.46
2.88
x
1O
1.56 x JQ3
1 J)
2.50
2.04
x
1()
4.74 x 10
i
2.5
2.47
x
10
3.90 x 10
28.0
2.63
3.19
x
1O
2.88 x io
26.0
2.70
3.07
x
1O
3.60 x JO
32.0
- 2.73
119
-------
TAbLE C—S. PERMEABILITY HISTORY FOR TH ONCALCARFOUS SMETTT C CLAY
SOIL PERMEATED WITh 1120 (O.O N CaSO 4 ) FOLLOWED BY ACETONE
(PORE VOLUME 399 c m 3 ; BYIP.AULIC CRADIE T = 361.6)
K
(cm sec )
T
(see)
Volume
(mis)
Pore
Volume
1.29 x ic1 9 1.382 x 10 51.5 0.46
1.02 x 10 6.912 x 10 20.5 0.31:
1 . 5 x iO 6.912 x 10 23.0 O.2R
1.15 x 1O 6.912 x 10 2i.0 0.23
1.10 x 1O 6.912 x ]0 22.0 0.17
1.25 x 1O 6.912 x 1O 25.0 0.11
1.02 x 6.912 1O 20.5 0.05
Fluid In changed from 1120 (O.OIN CaSO 4 ) to Acetone 0.0
1.30 x iO 6.912 x iO 26.0 C.06
1.12 x 1O 6. 12 x 22.5 0.12
1.10 1O 6.912 x 1O 22.0 0.18
7.49 x 1O 6.912 x 1O 15.0 0.21
7.24 io’° 6.912 x 10 14.5 0.25
6.49 x 13—10 6.912 x IO 5 13.0 0.22
5.49 x iO 6.912 x 1O 11.0 0.31
4.99 x 1O - 6.912 x 1O 10.0 0.34
4.00 x lO - 6.912 x 10 8.0 0.36
3.75 1O 6.912 x 10 7.5 0.37
3.75 x x 6.912 10 7.5 6.39
4.24 x icr’° 6.912 x 10 8.5 0.41
(Continued)
120
-------
TABLE C—S. CONTINUED
(c
K
sec 1 )
T
(see)
Volume
(mis)
Pure
Volume
4.00
x
iO O
6.912 x :o
8.0
0.43
4.00
x
i010
6.912 x 1O
8.0
0.45
7.66
x
10
5.184 x 10
11.5
0.48
i. 2
x
io 8
8.640 x
28.0
0.55
8.95
io8
1.080 x
28.0
0.62
6.71
10
3.600 x io
70.0
0.80
8.06
x
cr 7
3.600 x
84.0
1.01
121
-------
TABLE C—6. PER ABIL1Ty H3TO y FOR T 1E NONCALCAREOIJS S.IETIT:C CLAY
SOIL PER ’E .TED WITH 1120 (O.O1N CaSO 4 ) FOLLOWED BY THANOL
(PORE VOLUME 401 cm 3 ; HYDRAULIC GRADIENT = 361.6)
(cm
K
sec’)
1
(sec)
Volume
(mls)
Pore
Volume
1.37 x
iø
6.912 x
i0
27.5
0.46
1.40 x
iO
6.912 x
10
28.0
O. O
1.47 x
iO
6.912 :
1O 5
29.5
0.32
1.65 x
P 9
6.912 x
10
33.0
0.25
1.82 x
i0
6.912 x
10
36.5
0.17
1.57 x
6.912 x
10
31.5
0.08
Fluid
In”
changed
from H 2 0
(O.O1N
0a50 4 )
to. Methanol
0.0
1.72 x
io
6.912 ,
IO
34.5
0.09
2.31
1O
6.048 x
1O
40.5
0.19
6.79 x
i0
8.640 x
IO
7.0
0.23
2.18 x
io8
8.640 x
54 r
0.36
3.84 x
io8
4.500 x
5.0
0.38
3.66 x
10
4.200 x
io
44.5
0.49
1.17. x
iø 6
2.580 x
io
84.0
0.70
122
-------
TABLE C—i • PERMEABILITY HISTU.l? FOR THE NONCALCAREOUS SMETITIC CLAY
SOIL PERMEATED WITH H 2 0 (0.C IN CaSO 4 ) FflLL0 YED BY XYLENE
(PORE VOLUME = 409 cm 3 ; 1-IYDRJVJLIC GRADIENT = 361.6)
Effluent K T Volume Pore
H,O(%) Xylene(%) (cm sec 1 ) (St C) (mis) Volum’
100 0 1.63 x 5.184 x 1O 24.5 0.40
100 0 1.55 x 10 6.912 x 10 31.0 0.34
100 0 1.20 x icr 9 6.912 x 10 24.0 0.27
100 0 1.17 x i0 6.912 x 10 23.5 0.21
100 0 1.62 x io 6.912 1O 32.5 0.15
100 0 1.47 x 6.912 x 1o 5 29.5 0.07
Fluld In” changed fron, 1120 (0.OLN CaSO 4 ) t Xylene 0.0
100 0 1.30 x 10 6.912 x 1O 26.0 0.06
100 0 1.34 x j — 6.048 x i0 ?3. 0.12
“ ‘26 “ ‘74 7.59 x 1O— 8.1)40 x i 19.0 0.17
‘ ti 99 3.36 x 10 8.640 x 1) 69.0 0.38
Trace “400 >4.00 x 8.640 x iO’ >1000* >2.82
* Entire volume of the fluid chariber (‘ti ].iter) was releas d wIthin one
sampling period (24 hrs) resulting in air blowing through th2 corc.
123
-------
TABLE C—B. PERMEABILITY HISTORY FOR THE NONCALCAREOL S SMETITIC CLAY
FOIL PERMEATED WITH H20 (O. )1N CaSO 4 ) FOLLOWE.t) B ’ HEPTANE
(PORE VOLUME 405 Cm 3 ; HYDRAULIC GRADIENT = 361 ., )
tfflue ; : — K T Volume Pore
H 2 0(%) eptaue( ) (cm sec ) (see) (mis) Volume
ion 0 1.62 ‘ 1O 6.912 x 32.5 0.43
100 0 1.57 x 1fl° ‘.912 x 10 31.0 0.35
100 6 L.27 x io 6.912 x 10 25.5 0.27
100 0 1.47 x iO 6.912 x 10 29.5 0.21
100 0 1 6O x io— 6.912 x 10 32.0 0.13
100 0 ) .5O x 1O 5.18 x 10 22-5 0.06
“Fluid In” changed from H 2 0 (1.01 CaSO, 4 ) Heptane 0.0
100 0 1.33 x io 5.184 x 1O 20.0 0.05
100 0 1.50 x 10 6.912 x 1O 30.0 0.12
MB .B2 1.08 x iO 8.640 x 10 27.0 0. 9
Trace ‘1OO >-,.OO 1O e .6’ O x i0 4 1000* >2.65
tire volume of the fluid chamber ( 1 liter) as released within one
.,anpling peiod (24 hrs) resulting in air blowing through the core.
124
-------
TABLE C—9. PERMEABILITY HISTORY FOR THE CALCAREOUS ¶‘METITP’ CLAY
SOIL PERMEATED WITH H 2 0 (O.O1N CaSO 4 ) (CONTROL)
(PORE VOLIj E = 471 Cm 3 ; HYDRAULIC GRADIENT = 361.6)
K
(cm sec )
(sec)
(mis)
Pore
Volume
7.32 x iO 5.184 x 10 110.0 0 )
8.22 x j 9 5.184 x 123.5 0.26
“Fluid In” continued with H 2 0 (O.OLN CaSO 4 ) 0.0
8.94 x 1O 6.9 2 x I0 179.0 0.38
7.27 x 1O 6.912 x 10 145.5 0.69
7.47 x iO 6.912 x i0 5 149.5 i.e:
6.49 x 1O 6.912 x 10 130.0 1.28
5.77 x iO 6.912 x 10 115.5 1.53
5.42 x 6.912 x 10 108.5 1.76
125
-------
TABLE C—10. PERMEABILITY HISTORY FOR THE CA CAREOUS METITIC CLAY
SOIL &‘ERMEATED WI H H 2 () (O.O IN CaSO 4 ) FOLLO E0 BY ANILINE
FORE VOLUME = 454 Cm 3 ; HYDRA!JL3C GRADIENT 361.6)
EffIueu K
H 2 0(%) Aniline(I) (cm sec 1 )
T
(see)
Vo1ui ie
(mis)
Pore
Volume
iO O 0 :.29 x i c r 9 €.912 x io 146.0 0.51
100 0 .67 x IO 6.912 x 1 113.5 0.24
FIuid In” changed from H 2 0 (O.OIN case 4 ) to Aniline 0.0
100 0 7.04 x 10 3.456 x io 70.5 0.15
100 0 1.12 x 1O 1.728 x 56.0 0.27
8.63 x 1O 8.640 x io 216.0 0.74
‘30 4.80 x io8 8.640 x 1O 4 120.0
<10 >90 2.32 x 1O 8.640 x IO 58.0 1.13
Tr2ce ,100 2.52 x 1O .640 x iO 63.0 1.21
Trace ‘ 1OO 3.0$ x 10 8.640 x 10 77.0
Trace ‘ A00 3.28 x € ç . io 82.0
Trace ‘dOO 4.12 x io8 8.6! 0 x 103. 1.83
Trace %IOO 3.36 x io8 8.640 x IO 84.: 2.01
Trace ‘ ‘i( ) 4.60 x io8 $.6 O x 115.0 2.26
Trace ‘ ..10O 4.96 x i0 8 .64O x 124.0 2.53
Trace ‘ 1OO 3.96 x iO 8.640 x 99.0 2.7k
126
-------
TABLE C—il. PER’IEABILITY HISTORY FOR THE CALCARECUS SMETITIC CLAY
SOIL PERMEATED WITH H 2 0 (O.O1N CaSO 4 ) FOLLOWED BY ACETIC
ACID
(PORE VOLUME 48 c m 3 ; HYDRAULIC GRADIENT 361.6)
K
(cm ec 1 )
2.52 x io
5.19 x io—
Fluid In” changed
4.64 -
1.57 x io—
8.74 1o1)
4.50
2.00 x
10 _li
4.99 x
6.912 x
5.1E4 x
from
6.912 x
6.912 x
6.912 x
6.912 x
6.912 x
1.037 x
6.912 x
Pore
Vo lurje
O.2
0.17
0.21
0.28
0.32
0.34
0.34
0.35
0.35
T
(sec)
Volume
m ls)
10 50.5
10 78.0
(0.OIN C S0 4 ) to Acetic Acid
1 5 93.0
10 31.5
10 17.
10 9.0
10 4.0
io6 3.0
10 1.0
127
-------
TABLE C—12. PERMEABILITY HISTORY FOR THE CALCAREOUS SMETITIC CLAY
SOIL PERMEATED WITH 1120 (0.O1N CaSO 4 ) } ‘OLLOWED BY ETHYL} E
GLYCOL
(PORE VOLUME 478 cm ; HYDRAULIC GRADIENT 361.6)
K T Voleme Pore
(cm sec ) (see) (mis) Volurne
5.12 x io 6.912 x 10 102.5 0.39
4.22 x io— 6.9 2 x Jo 5 84.5 0.18
“Fluid Ir changed from IL’O (O.0I CaSO 4 ) to Ethylene Gly oi 0.0
6.07 x io— 6.°12 x 1O 121.5 0.25
5.29 x iO 1.728 x IO 26.5 0.31
5.39 x 8.640 x ‘o 13.5 0.34
1.60 x io 8.640 x JO 4 4.0 0.35
i.os x io 8 8.640 x 27.0 O.4C
8.79 x 8.640 x 22.0 0.45
1.12 x t0 8 8.640 x 28.0 0.51
1.12 x io 8 8.640 x IO 28.0 0.56
1.64 x io8 8.640 x io 41.0 0.65
2.32 x io 8 6.640 x Jo 4 58.0 0.77
5.27 x 1O 8.640 x 132.0 1.05
x io— 8 3.456 x 186.0 1.44
1.84 x io—8 3.456 x 184.0 1.82
1.71 io— 8 3.456 x 171.0 2.18
1.72 x io8 3.456 x 1Q 172.0 2.54
128
-------
TABLE C—13. PERMEABILITY HISTC Y FOR THE CALCAREOL’S SJ4ETITLC CLAY
SOIL PERNEATE!) WITH R 2 0 (O.OIN CaSO 4 ) FOLLOWED BY ACETONE
(PORE VOLUME = 455 cm 3 ; HYDRAULIC GRADIENT = 361.6)
K
(cm sec’ 1 )
T
(sec)
Volume
(mis)
Pore
Volume
2.82 x
3.44 x
1O
1O
6.912
6.912 x
1O
1O
56.5
69.0
0.46
0.33
4.14 x
1O
6.912 x
10
03.0
0.18
‘Fiuid
I’ ’
changed
from H 7 0
(O.O1N
CaS0 )
to
Acetone
0.0
4.32 x
iO
6.912 x
I0
86.5
;.I9
3.27 x
I0
6.912 x
10
65.5
0.33
9.99 x
1O
8.640 x
io
23.0
0.39
1.12 x
;o 8
8640 v.
28.0
0.45
>4.00 x10 7
8.640
1O 4
>1000*
>2.65
* Entire vc.uine of the fluid chamber ( i liter) was released within one
sampling period (24 hrs) resulting in air blowing through the core.
129
-------
TABLE C—14. l- RNEAhILITY HISTORY FOR THE CALCAREOUS SNETITIC CLAY
SOIL PER ATED WITH 1420 (O.O1’ CaSO 4 ) FOLLOWED BY METHANOL
(PORI VOLtfl ’IE 454 Cm 3 ; HYDRA JLJ1C GRADIENT = 361.6)
(cm
K
sec 1 )
“
(sec)
Volume
(mis)
Pore
Volume
4.70 x
iO
6.912 x
iO
94.0
0.39
5.43 x
1O
5.184 x
10
8i.S
0.18
“Fluid
In”
changed
from H 2 0
(0.OJN
caSO 4 )
tcs
Methanol
0.0
5.12 x
6.912 x
1O
102.5
0.22
5.19 x
10
8.640 x
Q4
13.0
0.25
>4.0 x
8.640 x
1fl
>1000*
>2.45
* Entire voiuae of the fluid chamber 1 liter) was released with 4 n one
sampling period (24 tirs) resulting in air blowing through the core.
130
-------
TABLE C- 15. PERHFABILITY HISTORY FOR THE CALCAREOUS SMETITIC CLAY
SOIL PER ATEI) WITH H20 (O.O1 C SO 4 ) FOLLOWED SY X’ILENE
(PORE /OLUME = 478 ct 3 ; HYDRAULIC GRADIENT 361.6)
Effli ent K
11 2 0(h) Xylene( (cn sec’ )
T
(sec)
Volume
(mis)
Pore
Volume
100 0 5.54 x 10 6.912 x 10 111.5 0.41
100 0 5.69 x 10 5.184 l0 85.5 0.18
“Fluid in” ch nged from (O.OIN Ca50 4 ) to xlen 0.0
100 0 5.40 : i0 3.456 X 1O 54.0 0.11
100 0 4.79 i0 8.640 x IO 12.0 0.14
‘ 26 ‘ 74 1.7(’ : lO 8.640 x 4 .5 0.23
%14 “. 86 4.5k : 10 5.280 x I0 ‘.O 0.24
Trace ‘ ,1OO 4.4 1O 3.600 x IO 462.0 1.21
131
-------
TABLE C—16. PERMEABILITY HISTORY FOR T F CALCARE3US SMET [ TIC CLAY
SOIL PERMEATED WITH H 2 0 (O.OIN CaSO 4 ) FOLLOWED BY }IEPTANE
(PORE VOLUME = 443 cm 3 ; HYL’RAULlC GRADIENT 361.6)
Effluent — K T Volume Pore
H 2 0(%) Iieotane(%) (cm se 1 ) (sec) (mis) V3lume
100 0 3.37 x 10 6.912 x 67.5 0.28
100 0 3.90 x 1O 5.184 x 1O 5 58.5 0.13
Fluid In changed from H 2 0 (O.O1N Ca50 4 ) t Heptane 0.0
100 0 3.86 x 5.184 x 1O 58.0 0.13
1.02 x 10 8.640 10 25.5 0.19
Trace “ 100 2.81 x 4.920 x io 4.0 0.20
‘ 96 2.48 3.900 x io 28.° 0.26
Trace ‘ 100 1.76 x 10’ 8.640 x 440.0 1.25
Trace ‘‘100 1.73 x 10 3.640 x 1O 432.0 2.23
132
-------
LABLE C—17. PERMEABIL T ’ HISTORY FOR THE MIXED CATION KAOLINITE CLAY
SOIL ER!4E TED WITh H 0 (O.OIN CaSO 4 ) (CONTROL)
(PORE VOLU? = 395 HYDRAULIC GRADIENT 61.1)
K
“
Volume
Pore
(cm sec )
(see)
(mis)
Volum ±
2.04 x .602 x 1t 16.0 G.14
1.79 x 1.765 x 1O 15.5 0.10
1.90 x IO 2.475 x 1O 25.0 0.06
‘FIuid In continued with H 2 0 (O.OIN caS0 4 ) 0.0
2.35 x 1o 8 6912 1O 79.6 0.20
2.47 x 6.912 x io 83.5 0.41
2.56 x i0 8 6.912 x 1O .36.6 0.63
2.43 x 6.912 x 10 82.1 0.84
2.76 x 6.912 x 10 93.3 1.08
2.23 x i08 6.912 x 10 75.6 1.27
2.06 x iü8 6.912 x ItJ 89.7 1.44
2.05 6.912 x 1O 69.4 1.62
2.06 x i08 5.184 x 1O 52.2 1.75
133
-------
TABLE C—18. PERMEABILITY HISTORY FOR THE MIXED CATION KAOL1 ITE CLAY
SOIL PERMEATED WITh H .0 (O.OIN CaSO 4 ) FCIJ.OWED BY ACETIC
ACID
(PORE VOLUME 381 c m 3 ; HYDRAULIC GRADIENT = 61.1)
(cm
K
sec’)
T
(sec)
Voluire
(mis)
Pore
Volume
1.27 x
io—8
3.367 x
io
21.0
0.10
1.32 x
10
2.475 x
1O
16.0
0.04
F1uid
In changed
from H 2 0
(O.O1N
CaSO 4 )
to
Acetic Acli
0.0
9.78 x
icr 9
6.912 x
1O
33.1
0.09
3.64
icr
6.912 x
12.3
0.12
3.55
1O
6.912 x
iO
12.0
0.15
3.40 x
io—
6.912 x
1O
11.5
0.18
3.55 x
iO
6.912 x
10
12.1
0.21
2.30 x
i c r 9
6.’)12 x
10
7.8
0.23
3.58 x
io—
6.912 x
10’
12.1
j.26
1.95 x
io
6.912 x
10
6.7
0.28
<1.0 x
10_li
1.382 x
106
0
0.28
134
-------
TABLE C—19. PERMEABILITY 1IIST( RY FOR THE MIXED c’ r o ; KAOL1NITE CL&Y
SOIL PER€ATED WITH 1120 (0.O!N CaB 0 4 ) FOLLOWED BY ANILINE
(PORE V0LU 395 HYDRAULIC GRADiENT 61.1)
Effluent K T Volume Pore
H2o(, ) Aniline(Z) (. m sec’) sec) (mis) Volume
100 0 1.52 x 1o8 33( 7 x io 25.0 0.11
100 0 1.49 x io8 2.475 x 1O 18.0 0.04
“Fluid In” cha ged from H 2 0 (O.0 N CaSO 4 ) to Aniline 0.0
100 0 1.09 x 6.912 x 10 36.9 0.09
iOO 0 j.47 x io 8 6.912 x 10 49.8 0.22
100 0 2.06 x o8 6.912 x 10 6 .7 0.40
100 0 2.21 x 10 6.912 x 10 74.8 0 58
%100 Trace 2.90 x i08 6.912 x 10 93.1 0.83
o 9O ‘ 10 5.68 x 1.728 1O 48.0 0.96
<10 <90 9.66 x 1O 1.728 x 10 81.7 1.16
Trice 1OO 1.05 x 1.728 x 1O 89.0 1.39
T ace 100 1.00 x i0 3.456 , 10 170.0 1.82
Jrace %100 2.51 x 10’ 1.668 x 10 205.0 2. 4
Trace oAOO 3.17 x io 1.206 x io 18.7 2.38
135
-------
TABLE C—20. P RMEA3ILITY HISTORY FOR THE MIXED CATION XAOLINITE CLAY
SOIL PERMEATED WiTH 1170 (O.O1N CaSO 4 ) FOLLOWD BY THYLEN1
GLYCOL
(PORE VOLUNE = 408 cm 3 ; HYDRAULIC GRADIENT 61.1)
K
T
Volum
Pore
(cm sec )
(sec)
(mis)
Voiu e
1.52 v 1O 3.367 x 25.0 O.1i
1.57 x io—8 2.475 x 10 19.0 0.05
“Fiud Ir. changed from 1120 (O.OIN CaSO 4 ) to Ethylene Glycol 0.0
1.66 x io 6.9 2 x 10 56.7 Q.j1
9.64 x i0 9 6.912 x 1O 32.6 0.22
5.44 x 10 ’ 6.912 x 18.4 0.27
4.17 x i0 6.9 2 x io 5 14.1 0.30
4.76 io 6.912 x iO 16.1 0.34
4.52 x 10 6.912 ‘ 1O 15.3 0.36
5.65 x 1O 6.912 x 1O 19.1 0.43
4.38 x icr 9 6.912 x 10 14.8 0.47
3.31 x icr 9 6.912 x 1O 11.2 0.50
2.54 x 6.912 x 10 8.6 0.52
2.36 x icr 9 8.640 x io . 1.0 0.52
136
-------
TABLE C—21. PERMEABILITY HISTORY FOR TH MIXED CATION KAOLINITE CLAY
SOIL PER>2 ATEO WITH H 2 0 (O.O1N CaSO4) FOLLOWID BY ACETONE
(PORE VOLUME 408 cm 3 ; HYDRA1.IL1C GRA1) 1 ENT 61.1)
K T Volume Pore
(c sec ) (sec) (m1 ) Volume
1.91 icr 8 1.602 io 15.0 0.14
1.97 x o”8 1.765 x 10 17.0 0.10
2.15 x 1O 2.475 x 10 26.0 0.06
Fluid In cha 1 ged from H 7 0 (O.O1N CaSO 4 ) Acetone 0.0
2.77 x 1O 3.456 x 10 46.9 0.11
2.06 x 1O 3.456 10 34.6 0.20
1.31 x 1C 3.456 x 10 22.L 0.25
1.24 x 10 3.456 x 10 21.0 0.31
1.43 x 10 3.456 x 1O 24.2 0.36
2.14 x 10 3.456 x 10 36.2 0.45
3.74 x 1O 1.728 x 10 31.6 0.53
6.15 x O8 8.640 x :o 26.0 0.59
1.e9 x iO 4.32’) x 40.0 0.69
3.55 x 1O 4.320 x 75.0 0.88
4.82 x 10 5.360 x 126.5 1.19
5.26 x icr 7 2.270 x 10’ 58.5 1.33
137
-------
TABLE 0—22. PERMEAbILITY HISTORY FCR THE MIXED CATION KAOLINITE CLAY
SOIL PERNEATEI) WITH 1120 (0.OIN CaSO 4 ) FOLLOWED BY t EThANOL
(POk(F VOL J1 = 395 Cm 3 ; H’YD11AULIC ( RPr)IENT = 61.)
Pore
Vo lUflk
(cm sec
(sec)
(r .i l )
1.43 x
i(r8
3.285 x
1O
23.0
0.10
1.49
i08
2.475 x
10
18.0
0.04
“Fluid
In”
changed
from M 2 0
(0.OJN
CaSO 4 )
Methanol
0.0
2. 9 x
ic—8
3.456
io
37.0
3.0
1.68 x
10
3.450 x
io
28.5
0.16
1.85 x
i08
3456 x
i0
31.3
0.24
c .44 x
io 8
3.456 x
10
92.1
0.48
1.24x
iO
3.456 x
1O
209.1
1.01
1.57 x
i0
8.060 x
IO
62.0
1.16
3.04 x
5. J2 x
IO
1(r 7
- 7.740 <
6.430 x
10’
115.0
158.0
1.46
1.86
)
138
-------
TABLE C--23. PERMEABILITY HISTORY FOR THE MiXED CATION KAOLI iTE CLAY
SOIL. PERMEATED WITH H 2 o (0.OIN CaSO 4 ) FOLLOWEE EY XYLENE
(PORE VOLUME 384 cm 3 ; H’fl)RAULIC GRADIENT = 61.1)
Effluent
(an
K
sec’)
T
(;ec)
Volune
(mis)
Pore
Volume
1 120(A)
Xyiene(%)
1Cc)
0
1.78
x i08
1602
x 1C 5
0.13
100
0
1.75
x 10_S
1.755
x 10
15.0
0.10
100
0
1.77
x i 8
2.475
x 1O
21.5
0.06
•Fluid
In” changed
from
(fl.O1N
CaSO 4 ) to
Xyiene
0.0
100
0
1.66
x io—8
3.456
x )O
28.1
0.07
‘1C0
Trace
2.14
. 1O
1.296
x i0
13.6
0.11
Trace
“400
3.17
x IO
4.320
x
67.0
0.28
Trace
10O
7.66
x 10
3.600
x 10
13.5
0.32
Trace
‘\‘lOO
8.29
x iO
3.600
x
14.6
0.36
Trace
“ ‘100
9.65
x i0
3.600
x IO
17.0
0.40
Tract
10O
1.90
x 106
3600
x
13.5
0.49
Trace
1400
2.36
x JØ6
3.600
x
41.5
0.60
139
-------
TABLE C—24. PER1 1EADILITY HISTORY FCi THE MIXED CATION KAOLINITE CLAY
SOIL PERMEATED WITH H 2 0 (O.OIN CaSO 4 ) FOLLOWED BY HEPTANE
(PORE VOL JME = 378 cm 3 ; HYDRAULIC GRAI)TENT = 61.1)
Effluent K
1120(h) Heptane(%) (cm sec )
T
(sec)
Voium€
(mis )
Pore
Volume
100
0
1.78
x 1r
1.602
x 10
14.0
0.14
100
0
1.86
1.755
x 10
16.0
0.10
100
0
1.98
x 1O
2.475
x 10
24.0
0.06
Fluid
In changed
from
1120 (O.0 N
caSO 4 ) to
Heptane
0.0
100
0
3.36
x iO 8
2.592
x 1O
42.6
0.11
Trace
‘ dOO
1.25
x iø
1.728
x io
106.1
0.39
Trace
‘ 1OO
1.64
x 10
3.600
x io
29.0
0.47
Trace
1O0
3.58 x 1O
1.442 x
252.3
1.14
140
-------
TABLE C—25. PEt MEABILITY HISTORY FOR ThE MIXED CATION ILLITE CLAY
SOIL PERMEATED WITH 1120 (O.OIN C iSO 4 ) (CONTROL)
(P01 E VOLtJME = 398 cm 3 ; HYDRAULIC GRADIENT = 61.1)
K T Volume Pore
(cm sec ) (see) (mis) Volume
1.03 x IO 6.246 x 10 31.5 0.35
6.55 x 9.576 x 10 30.7 0.28
6.19 x io— 1.442 x io6 43.7 0.20
1.05 x i08 6.912 iO 35.4 0.09
Fluid In continued with 1120 (O.OIN CaSO 4 )
8.46 x io 9 3.456 x fö 5 14.3 0.04
1.01 x 1O 6.912 x 1O 5 34.0 0.12
1.17 x 1O 6.9i2 x 1O 39.4 0.22
1.36 x 6.912 x 10 45.9 0.34
1.07 x i r 8 6.912 x 10 3 .O 0.43
9.88 x IO 6.912 x 10 33.4 0.51
1.01 x i08 6.912 x 1O 34.0 0.60
1.05 x 108 6.91 x 10 35. 0.68
1.24 x 1o 8 6.912 x 1U 42.0 0.79
1.04 x icr 8 6.912 x 10 35.0 0.88
1.07 x i c r 8 f.912 x 10 36.2 0.97
1.28 icr 8 f 912 x JO 5 43.3 1.08
1.09 x icr 8 6.912 x 10 36.9 1.17
1.30 x iO8 6.91? x io 43.9 1.28
1.45 iO8 E)12 x 10 49.0 1.40
(Continued)
141
-------
TAPLE C—25. CONTI [ JED
K T Volume Pore
(cm sec 1 ) (sec) (nils) Volume
1.48 x i c r 8 6.912 x 10 49.9 1.53
i. i icr 8 6.912 x 13 54.5 1.67
1.69 icr 8 6.912 x 10 57.0 1.81
1.83 x icr 8 6.912 x 10 61.9 1.96
1.99 x 1O 6.912 x 10 67.1 2.13
2.02 x i0 6.912 1O 68.2 2.30
142
-------
TABLE C—26. PERMEABILITY HISTORY FUR THE MIXED CAT1C N ILLITE CLAY
SOIL. PERMEATED WITH H 2 0 (O.OIN CaSO 4 ) FOLLOWED BY ACETIC
ACID
(PORE VOL JME = 405 cm 3 ; HYDRAULIC CRADI NT 61.1)
K
T
Volume
Pore
(cm sec’ )
(sec)
(mis)
Volutne
7.85 x io— 9.576 x i0 5 36.8 0.26
6.23 x io— 1.442 x 44.0 0.17
7.84 x iO 6.912 x i0 5 26.5 0.07
“Fluid In” changed fiom the H 2 0 (O.O1N CaSO 4 ) to Acetic Acid 0.0
8.01 x 10 6.912 x 27.1 0.07
5.83 x 1O 6.912 x 1O 19.7 0.12
7.87 x —9 6.912 x io 26.6 0.18
7.07 x icr 9 6.912 x iO 23.9 0.24
7.07 x icr 9 6.912 x 1O 23.9 0.30
7.93 x icr 6.912 x 10 26.8 0.37
5.56 x icr 9 6.912 x 1O 18.8 0.41
5.92 x io— 6.912 x iO 20.0 0.46
5.83 x i c r 9 6.912 x 1O 19.7 0.51
3.85 x 10 6.912 x iO 13.0 0.54
3.22 x icr 9 6.912 x iO 10.9
1.60 x icr 9 6.912 x 10 5.4 3.58
1.89 x icr 9 6.912 x 1O 6.4 0.60
1.48 x icr 9 6.912 x iO 5.0 0.61
1.18 x i0 9 6.912 x 10 4.0 0.62
7.69 x icr’ 0 6.912 x 2.6 0.62
(Continued)
‘43
-------
TABLE C—26. CONTINUED
(cm
K
sec )
T
(see)
Volume
(mis)
Pore
Volume
9.47
x
i 0
6.912 x 10
3.2
0.63
1.69
x
i0
6.912 x iO
5.7
0.65
1.83
x
1O
6.912 x 10
6.2
O.6h
1.69
x
iO
6.912 x 10
.7
O.6b
144
-------
TABLE C-27. PERMEABILITY HISTORY FOR THE MIXED CATION ILLITE CLAY
SOIL PERMEATED WITH H 2 0 (O.O IN CasO ) FOLLOWED BY ANILINE
(PORE VOLU}4 = 402 c m 3 ; HYDRAULIC GRADIENT 61.1)
Ef
fluent
Anili e( ,)
(cm
K
sec )
T
(sec)
Volume
(mis)
Pore
Volume
H 7 (%)
100
0
6.14
x iO
2.592 x 1O
7.8
0.13
100
190
0
0
2.88
.55
x io 9
x 1O
9.576x JO 5
1.442 x io6
13.5
18.0
0.11
0.O
100
0
3.91
x iO
6.912 x
13.2
0.03
Fluid
In”
changed
from
H 2 0 (O.O IN
C ISO 4 ) to Aniline
0.0
100
0
6.21
x io
3.456 x l0
0.5
0.03
100
0
1.2!
x j ”8
8.640 x
5.1
0.04
5O
‘ 5O
1.26
x 1o 7
4.320 x
26.5
0.10
MO
‘ . .9O
1.28
x io
4.320 x
27.0
0.17
1 5
-------
TABLE C—28. PERMEABILITY HISTORY FOP. THE MIXED CATION ILLITE CLAY
SOIL PERMEATED .YITH 1120 (O O1N CaSO 4 ) F0LL )W1D Y ETHYLENE
GLYCOL
(PORE VOLUME 4O cm 3 ; HYD AUL1C GRADIENT = 6k.l)
K
T
Vo luiae
Pore
(cm sec )
(see)
(mis)
Volume
7.17 x icr 9 1.710 10 6.0 0.Zd
8.47 x ic r 9 4.536 x 106 18.8 0.26
5.31 x io’- 9.576 x 1O 24.9 0.21
5.03 x icr 9 1.442 x io6 35.5 0.15
7.78 x icr 9 6.912 io 26.3 0.07
“Fluid In” changed from the 1120 (0.O1N CaSO 4 ) to Ethylene Ulycol 0.0
8.05 x io— 6.912 x 1a 27.2 0.07
7.28 x 10 6.912 x 10 24.6 0.13
7.69 x io— 6.912 x 1O 26.0 0.19
5.50 x i c r 9 b.9 12 x 18.6 0.24
4.64 x icr 9 6.912 x 10 15.7 0.28
3.82 x icr 9 6.912 x 10’ 12.9 0 31
3.55 x icr 9 6.912 x 12.0 0.34
3.11 x io— 6.912 x 10 10.5 0.37
3.99 x iO 6.912 x 10 13.5 0.40
2.87 x io— 6.912 x i P 9.7 0.42
2.40 x io— 6.912 x 8J 0.44
2.19 x io 6.9t2 x 1O 7.4 0.46
.98 x ic r 9 6.912 x 6.7 0.48
2.81 10 6.912 x 9.5 0.50
(Continued)
146
-------
TABLE C—28. CONTINUED
(cm
K
sec’)
T
(see)
V 1ume
(mis)
Volume
1.51
x
io—
6.912 IO
5.1
0.51
9.76
x
1C
6.912 x 1
3.3
0.52
1.51
x
1O
6.912 x 10
5.1
0.53
1.57
x
1i
6.912 x 10
5.3
0.55
1.48
x
i0
6.912 x iO
5.0
0.56
1.63
io
6.912 x 1O
5.S
0.57
1.57
x
1O
6.912 x 10
5.3
0.59
14?
-------
TABLE C—29. PERMEAE1LITY HISTORY FOR THE MIXED CATION ILLITE CLAY
SOIL PERI U ATED WITH 1120 (O.OIN GaSO 4 ) FOLLOWED BY ACLTONE
(PORE VOLUME 399 ci 3 ; HYDRAULIC GRADIENT 61.1)
K
T
Velume
Pore
(cm secT’)
(sec)
(mis)
Voiume
2.57 x 10 . .O24 x io6 38.0 0.12
3.55 x i0 6.912 x 10 12.0 0.03
•‘Fluid In changed from the 2 O (O.O1N CdSO 4 ) to Ac ton 0.0
6.89 x iO 6.912 x i0 23.3 0.06
5.77 x 1O 6.912 x 10 19.5 0.11
5.53 x 1O 6.912 x 10 18.7 0.15
4.73 x 1O 6.912 x 1O 16.0 0.19
4.14 x iO 6.912 x 10 14.0 0.23
3.85 ; iO 6.912 x 10 13.0 0.25
3.37 x 10 6.912 x 10 11.4 O.2
3.52 x icr 9 6.912 x 10 11.9 0.32
4.50 x 1O 6.912 x 10’ 15.2 0.36
3.43 x 1O 6.912 x 10 11.6 0.39
3.55 x i0 6.912 x 10 12.0 0.42
4.67 x icr 9 6.912 x 10 15.8 0.46
1.43 x i0 1.728 x 10 12.1 0.49
2.38 x icr 8 1.728 x IO 20.1
3.90 x io8 1.728 x 10 33.0 0.62
8.45 x icr 8 1.728 x 10 71.5 0.80
1.17 x icr 8 2.160 x 124.1 1.11
(Continued)
148
-------
TABLE C-29. CONTIXUED
(cm
K
sec 1 )
‘
(sec)
Volume
(mis)
Po:e
V3lume
7.9
1o
1.080 10
42.1
1.22
8.24
x
10
3.600 x
14.5
1.25
8.41
x
i0
3.6O0 x io
14.8
1.29
8.92
x
10
3.600 x
15.7
1.33
149
-------
TABLE C—30. PERMEM ILITY HISTORY FOR TIlE MIXED CATION ILLITE CLAY
SOIL PERMEATED W T TH H 2 0 (O.O1N CaSO 4 ) FOLLO EO BY ?€THANOL
(PORE VOLUME 408 cm 3 ; HYDRAULIC GRADIENT = 61.1*)
Effluen ___ K
H 2 0(7.) M thano!(%) (cm sec’)
T
(sec)
Volume
(mis)
Pore
Volume
100
0
7.40 x
2.592 x 1O
9.4
0.20
100
0
4.31 x io—
9.576 x 10
20.2
0.17
100
C
4.28 x icr 9
1.442 x 1o 6
30.2
0.13
100
0
6.18 x io—
6.912 x 1O
20.9
0.05
Fluid
In” chaaged
from H 2 0 (0 O1!
aso 4 ) to Methanol
0.0
100
0
6.89 x icr 9
6.912 x iO
23.3
O.O
100
0
5.74 x i0
6.912 x 1O
19.4
0.10
100
0
6.39 ‘ 1O
6.912 x lO
21.6
O. 6
100
0
5.44 x 1O
6.912 x 1O
18.4
0.20
100
0
5.65 x i c r 9
6.?t2 x IO
19.1
0.25
100
0
6.66 x H 9
6.912 x 10
22.5
0.30
100
Trace
9.23 x i0
6.912 y. 10
31.2
0.38
97
3
2.16 x
3.456 x 10
36.5
0.47
66
34
3.60 x i c r 8
34
óO.8
0.62
47
53
5.45 x icr 8
2.592 . 10
69.2
0.79
39
61
7.38 x icr 8
8.640 x io
31.2
0.87
34
66
1.19 x io—
8.640 1O
50.2
0.99
29
71
1.96 x 1O
S.640 x iü
83.1
1.19
24
76
2.96 x 10
4.320 x io
62.5
1.35
21
79
3.19 x icr 7
2.160 x
33.8
1.43
150
-------
TABLE C—30. CONTINUED
Eff’ nt
H)0(%) Metha ol(%)
K
(cm sec )
T
(sec)
Volume
(mis)
Pore
Volume
21
79
3.96 x io
2.60 x 1O
42.0
1.53
21
79
5.9 x 10
2.160 x
55.0
1.b7
ND
ND
9.76 x i0 8
6.912 x 1O
10.0
1.69
ND
NI)
1.67 1o 7
6.912 x 10
17.1
1.74
ND
ND
3.55 x i0
6.912 x 1O
36.4
1.83
ND
ND
6.66 x iO
6.912 x 1O
68.2
1.99
ND
ND
1.66 x io6
2.590 x 1O
63.7
2.15
ND
ND
2.43 x 10
1.728 x 10
62.1
2.30
ND
ND
4.78 x io6
2.163 x
15.3
2.34
ND
ND
].19 x IO
2.loO x
38.1
2.43
ND
ND
1.65 10
2.160 x
52.7
2.56
N 1 ) = Not determined.
Hydraulic gradient (H) cha’ ged from 61.1 to 1.85 at PT = 1.67.
151
-------
TABLE C-31. PER} Et BILITY HISTORY FOR THE MIXED CATION ILLtTE CLAY
SOIL PERNEATED WITH H 2 0 (O.O1N CaSO 4 ) FOLLOWED BY XYLENE
(P3RE VOLL T M 405 cm 3 ; HYDRAULIC GRADIENT 61.1)
Effluent
(cm
K
sec )
T
(sec)
Volume
(mis)
Pore
Volume
H 2 0(%)
Xylene(%)
100
0
3.35
x iO
1.710 x 10
2.8
0.14
100
0
5.41
x iO
4.536 x 10
12.0
0.14
100
0
2.54
x
9.576 x 1O
11.9
0.11
100
0
2.76
x 1O
1.442 x io6
19.5
0.08
100
0
3.49
x 10
6.912 x 10
11.8
0.03
Fluid
1n’ changed
from
1120 (O.O1N
ca80 4 ) to Xylene
0.0
100
0
7.34
x io 9
3.456 x 10
12.4
0.03
‘ .58
2
8.25
x 1O
4.320 x
17.4
0.07
Trace
‘ lOO
1.33
x 10’
4.320 x
28.0
0.14
Trace
lOO
2.61
x i06
1.800 x IO
23.0
0.20
Trace
O0
2.61
x io6
1.800 x IO
23.0
0.26
Trace
‘ 100
2.27
x i06
1.800 x io 3
20.0
0.31
Trace
“‘100
1.65
x i06
3.60G x io
29.0
0.38
152
-------
TABLE C—32. PER1 fEABILLTY HI 3TORY FOR THE MIXED CATION ILLITE CLAY
SOIL ERHEATED WITH 1120 (O.O IN CaSO 4 ) FOLLOWED BY HEPTAI4E
(PORE VOLUME 413 cm 3 ; HYDRAULIC GRADIENT 61.1)
Eff1u nt
H 2 (b) Heptane(%)
(cm
K
sec )
T
(sec)
Volume
(mis)
Pore
Volume
100
0
4.78
x
9.576
x 10
22.4
0.15
100
0
3.12
x 1O
1.442
x 1O
22.0
0.09
100
0
4.88
x
6.912
x 1O
16.5
0.04
“Fluid
In” changed
from
1120 (O.OIN
CaSO 4 ) to
Heptane
0.0
100
0
5.71
x 1O
S. 184
x 10
14.3
0.04
‘ 50
‘ 50
5.88
x 10
4.320
x
12.4
0.07
Trace
‘ 1O0
4.20
x 1o 6
1.830
h iO
37.0
‘.1S
Trace
‘ 1OO
4.77
x iO 6
1.800
x 1O 3
42.0
0.26
Trace
1OO
5.11
x i0 6
1.800
x IO
45.0
0.37
Trace
“400
5.63
x iø6
3.600
x
99.0
0.61
Trace
‘ .1OO
5.80
x io—6
3.600
x
102.0
0.85
Trace
“100
6.33
x 10—6
3.600
x IO
115.0
1.1
Traca
“100
6.46
x i06
2.100
x IO
66.5
1.29
Trace
“‘100
4.02
x io—6
6.600
x 1O
130.0
1.61
153
------- |