United States
 Environmental Protection
 Agency
 Municipal Environmental Research
 Laboratory
 Cincinnati OH 45268
Research and Development
EPA-600/S2-81 -122  July 1981
 Project  Summary
Liners  of  Natural   Porous
Materials  to  Minimize
Pollutant  Migration
Wallace H. Fuller
  This study concerned the relative
effectiveness  of  natural  low-cost
liners—(a)  crushed  limestone,  (b)
clayey soil, (c) hydrous oxides of iron,
and  (d)  crushed  pecan  hulls—to
minimize the migration of beryllium,
cadmium,  chromium,  iron, nickel,
zinc, and total organic carbon consti-
tuents of municipal solid waste landfill
leachates. Several leachate variables
such as aqueous  dilution,  aeration,
pH, and flux were also studied for their
effect on movement of metals through
11  representative  U.S.  soils.  The
research  was  conducted  on  a
laboratory scale with the use of soil
columns as a first step in screening for
potential liners and leachate manipu-
lation practices.
  This Project Summary was develop-
ed by EPA's Municipal Environmental
Research Laboratory, Cincinnati, OH,
to announce  key findings of the re-
search  project  that is  fully  docu-
mented in a  separate report of the
same title (see Project Report ordering
information at back).
Introduction
  When  landfills are  not completely
impermeable then underlying ground-
water may be contaminated by leachate
constituents if these are not adequately
retained  by soils between the landfill
and groundwater. Research on indus-
trial waste disposal has centered on use
of  manufactured products such  as
plastics and cementing roadbed mate-
rials (such as asphalt and concrete) to
alleviate the  leaching  problem  by
completely preventing liquid movement
out of the landfill. Little attention has
been given to use of natural low-cost
materials  as  barriers for minimizing
pollution migration by retaining con-
taminants from liquids as they pass out
of the landfills.
  The objectives of the project were to
  1   Identify further those parameters
     in soil and municipal solid waste
     landfill leachate that influence
     movement  of contaminants
     through soils.

  2.  Evaluate crushed limestone as a
     liner to limit metal movement from
     landfills.

  3.  Evaluate hydrous oxides of iron,
     natural clays, and pecan hulls as
     liners to limit metal and organic
     constituent movement from land-
     fills.

  4.  Study the use of control of  flux
     (flow  rate) to limit  migration of
     metals and organic carbon consti-
     tuents through soils.

  The elements that were considered
include: arsenic (As),  beryllium (Be),
cadmium (Cd), chromium (Cr), iron (Fe),
nickel (Ni), selenium (Se), vanadium (V),
and zinc (Zn)  as well as total organic
carbon (TOC).

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Materials and Methods
  Table 1 presents the properties of
some of  the  soils  used in  the study.
Leachate was generated in two 4000-L
tanks that had been packed with typical
municipal solid waste (MSW). The soils
were uniformly packed into PVC  cyl-
inders. MSW leachate was perfused
through soil using a peristaltic pump
regulated to deliver fixed fluxes ranging
from 1.2 to 17.1 cm/day. The effluents
were collected and analyzed each hour
by use of a  fraction collector. Where
necessary, leachates were enriched to a
concentration of  100  mg/L for  the
element  in  question  to  ensure that
metal migration would occur through
the soil columns. The following barrier
materials were considered:

Limestone
  Unsieved,   commercial-grade  lime-
stone (98%  CaC03) from  Cedar Bluff,
Kentucky, was  used. The  limestone,
developed for commercial agricultural
soil application, has a particle density of
2.72 g/cm3 and a fairly broad range of
size distribution. When used as a leach-
ate barrier, the Cedar Bluff limestone
was compacted to an average density of
1.67 g/cm3.

Pecan Hulls
  Pecan hull  waste from  a  local com-
mercial pecan  production  enterprise
was further  crushed by  hand  in  a
ceramic mortar to pass a 2-mm sieve. In
this form, it was layered over soil in a
column.

Hydrous Oxides of Iron
  Iron  rust was scraped from a gas
boiler, ground in a steel mortar to pass a
0.5-mm sieve, and used without further
alteration. No carbon was identified as a
contaminant.   Also,   waste  ferrous'
sulfate was sprinkled on some columns
and allowed to oxidize.

Results

  Layers of crushed limestone retarded
movement of  contaminants  through
soil. Concentrations  of  contaminants
increased more rapidly in effluents from
untreated soil columns than they did in
effluents  from limestone-treated
columns. See Figure 1 for an example of
the effect of movement on Fe. The retar-
dation of Cr movement by limestone and
soil combined was greater than the sum
of the effects of each acting alone (Table
2).
  Iron hydrous oxide applied as iron rust
was an  effective  barrier,  retarding
movement of contaminants so that they
appeared  much later in effluents  from
treated columns than in effluents  from
untreated columns. Figure  2 shows an
example of this effect on two soils for Cr
and Ni. Waste ferrous sulfate treated
soils  likewise retained metals  from
leachate, but increased levels of iron
were  noted in column  effluents. Be-
cause  of this leaking effect,  ferrous
sulfate waste is not recommended as a
liner.  No iron leakage was noted from
the iron rust treated columns.

Conclusions

 •  The composition of MSW leachate
     (particularly with reference to TOC
     content, total  ion  concentration,
     and pH) exercises a profound in-
     fluence on retention of the metals
     As, Be, Cd, Cr, Fe, Ni, Se, V, Zn,
     and the more  common elements
     Ca, K, Na, and Mg.

  •  An abundance of electron donors
     (TOC  and   Fe+2)  in  leachates
     combined with acidity reduction,
     either naturally by'aging or by in-
     serting a  limestone  barrier,
     encourages  chromium  retention
     by soil through the mechanism of
     valency change  of CrVI to Crlll.
     Crlll, a cation,  is  less mobile than
     CrVI, an anionic  form.

  •  When placed in  layers over soil,
     crushed agricultural limestone;
     —significantly slows the rate of
       movement of As, Be, Cd, Crlll,
Table 1.     General Characteristics of Some of the Soils


Soil
Series

Soil
Paste,
pH
Cation
Exchange
Capacity
meg/WOg
Elec.
Cond. of
Extract,
fjmhos/cm
Column
Bulk
Density, Silt,
g/cc %
Soil
Surface
Clay, Area,
% mz/g


Predominant
Clay Minerals*
Davidson      6.4         9         169        1.40       20        52        51.3   Kaolinite

Mohave       7.8        12        510        1.54       28        40       127.5   Mica,
  (Ca)                                                                                 montmorillonite

Ava           4.5        19         157        1.45       60        31        61.5   Vermiculite,
                                                                                      kaolinite

Anthony      7.8         6        328        2.07       14        15        49.8   Montmorillonite.
                                                                                      mica

Mohave       7.3        10        615        1.78       37        11        38.3   Mica, kaolinite

Kalkaska      4.7        10        237        1.53        4         5         8.9   Chlorite, kaolinite

Wagram      4.2         2        225        1.89        8         4         8.0   Kaolinite, chlorite
* Listed in order of dominance.

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     1.0 .-
      .8

      .6

      .4


      .2
/Mohave Sandy Loam
  —• No Limestone
  -—  Limestone
/Ava Silty Clay

  •s
 .8


 .6

 .4


 .2


 .01
1.0

 .8


 .6

 .4


 .2


 .0
              Mohave Clay Loam
           I   i  L/U>|
                                             -  i
                                              I
                                              i
                                             -i
                                             T Wagram Loamy Sand
                                              I   i  i
                 t  Anthony Sandy Loam
                                      j	i
                                   Kalkaska Sand
                     10   14   18   22   26   2    6   JO

                             Pore Volume Displacement N
                                            14   18   22
 Figure 1.  Effect of crushed limestone la yered (2 cm) o ver six soils on the retention
            of Fe from MSW landfill Leachate II.
       Fe, Ni, Se, V, and Zn through
       soil,
     —affects metal retention  in the
       following  order  of decreasing
       values:
        Crlll>Se>As>V>Be>Zn>Ni>
             Fe>Cd>CrVI>TOC
     —exhibits metal retention  effects
       several   times   greater  than
       when limestone or soil alone is
       used (a synergic effect),
     —is poorly effective for TOC atten-
       uation in MSW leachate, and
     —does  not  effectively  attenuate
       the TOC in MSW leachate.


Thick layers of crushed limestone (5,10,
15 cm) provide a more effective barrier
                       than thin layers (2 cm) for MSW leach-
                       ate metal migration through soils.

                         •  Leachate flux  through  soil
                            columns has a significant  influ-
                            ence  on  attenuation of certain
                            metal lions  in MSW leachates
                            when flow rates  are between 2
                            and 12 cm/day. The effect of other
                            leachate variables such  as pH or
                            concentration of TOC or inorganic
                            salts  so  overshadows  the  flux
                            effect that it is difficult to separate
                            flux effects on metal attenuation
                            from the effects of other variables.

                         •  Hydrous oxides  of  iron,  either
                            formed  by spraying soils or sands
                            with ferrous  sulfate or  iron rust
   placed as a 1-mm layer over soil,
   delay migration of soluble Fe and
   Cd.

•  Other studies indicate that natural
   clay soils  (20%<2// clay),  com-
   pacted  to  known  homogeneous
   densities with  sufficient sodium
   salts (Na2COa,  NaCI) to provide
   greater  than  20%  of  cation-
   exchange  capacity  saturation,
   may be so manipulated as to pre-
   vent  downward  movement  of
   MSW  leachate, solution, and all
   pollutants nearly completely.

•  The data reported here (except the
   item above) are the result of labor-
   atory  studies   only  and  are
   intended as a first step in screen-
   ing potential liners.  They'do not
   form a  sufficient  basis for  exact
   liner design. The complex nature
   of the interactions of soil, leach-
   ate,  and pollutants require  field
   testing before  final applications
   can  be recommended.
                        Recommendations
                         •  Because soils are highly stratified
                             under  natural conditions,  soils
                             underlying the disposal site must
                             be made as homogeneous as prac-
                             tical by mixing and compacting to
                             ensure  minimum  migration  of
                             pollutants from solid waste land-
                             fills.

                         •  The use of crushed  limestone
                             should  be  considered   for
                             minimizing  movement of poten-
                             tially hazardous pollutants such as
                             As, Be, Cd, Cr, Fe, Ni,  Se, V, and
                             Zn.

                         •  Layering limestone over soil as a
                             barrier  between  MSW  landfill
                             leachates  and geological mate-
                             rials  underlying  the  landfill   is
                             recommended over mixing lime-
                             stone and soil together or mixing
                             limestone with solid waste.

                         •  A  layer  of  crushed  limestone
                             about  15 cm (6 in.) thick is  sug-
                             gested   as  minimum   at most
                             disposal sites, but specific wastes
                             and soils should be tested before a
                             precise thickness is finally selec-
                             ted for a given site.

                         •  The particle sizes of crushed agri-
                             cultural  limestone   that  are

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                                             size  distribution,  (2)  optimum
                                             thickness, (3) cementation
                                             characteristics,  (4)  channeling,
                                             and (5) mechanics of placement.

                                          The full report was submitted in ful-
                                        fillment of Grant No.  R 803988 by the
                                        University  of  Arizona,  Tucson, AR
                                        85721, under  the sponsorship of the
                                        U.S. Environmental Protection Agency.
     generally commercially available
     appear to be suitable for use, but
     field verification studies are sug-
     gested.   The   most  desirable
     particle sizes range from coarse
     gravel to medium sand (5 to 0.05
     mm), with most of the material in
     the middle group.

 •   High-quality limestone is recom-
     mended because polluting metals
     may otherwise be present and be-
     cause, when compared with lime
     (CaCOs),   dolomite  (MgCOa)  is
     highly insoluble and quite unreac-
     tive at field temperatures.

 •   Field studies should be conducted
     to verify the usefulness of crushed
     agricultural limestone and should
     include evaluation of (1)  particle

Table 2.    Effect of Limestone Alone and Limestone Layered Over Soils on the
           Attenuation of Cr in MSW Landfill Leachate II*

Series
Soil
Clay. %
Ratio of
Cr in
Influent and
" — Effluent.
pH C/Co
#Pvd* Number When Cr Concen-
tration in Effluent is at
C/C0 Given in Col. 4
Limestone Soil Soil and
Alone Alone Limestone
 Davidson c
                52
6.2
0.13
          28
   Ava sicl      31
                          4.5       0.38
                               21
                                49
 Anthony si      15
                          7.8        1.00       57
                               39
                               125
  Mohave si      11
                          7.3      0.76       46
                               25
                               144
  Kalkaska s
                          4.7
          1.00
           57
17
111
  Wagram s
                          4.2
          1.OO
           57
15
109
* Leachate II had a pH value of 4.0, TOC of >3000, and Fe of 300 ppm.
*Pvd, Pore volume displacement number, is the number of pore volumes of
 leachate that have passed through the column.

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                                                            Treatments
                                                         	Soil Alone
                                                         	Soil FeO
                   6  8  10 12  0  2   4   6   8  10  12  14  16  18 20
                       Pore Volume Displacements

Figure 2. Effect of the hydrous oxides of iron precipitated on Anthony si and
          Wagram s on attenuation of CrVI and attenuation ofCrVlandNiofMSW
          Leachate I.
 Wallace H. Fuller is  with  the Arizona Agricultural Experiment Station, The
   University of Arizona, Tucson, AZ 85721.
 Mike H. Roulier is the EPA Project Officer (see below).
 The complete report, entitled "Liners of Natural Porous Materials to Minimize
   Pollutant Migration," (Order No. PB 81-221 863; Cost:  $9.50, subject to
   change) will be available only from:
        National Technical Information Service
        5285 Port Royal Road
        Springfield, VA 22161
         Telephone: 703-487-4650
 The EPA Project Officer can be contacted at:
        Municipal Environmental Research Laboratory
        U.S. Environmental Protection Agency
        Cincinnati, OH 45268
                                                                                 0 as.aOVERNMEKTmiKTlNOOFFICE: 1«61 -757-012/7236

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