The Effect of Soils on the Permeation of Plastic Pipes by Organic Chemicals

Author(s): Thomas M. Holsen, Jae K. Park, Laurent Bontoux, David Jenkins and Robert E.
Selleck
Source: Journal (American Water Works Association), Vol. 83, No. 11, Health Effects
(NOVEMBER 1991), pp. 85-91
Published by: American Water Works Association
Stable URL: http://www.jstor.org/stable/41293557 .
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The

Effect

on

the

of

Plastic

by

Organic

of

Soils

Permeation
Pipes
Chemicals

Thomas M. Holsen, Jae K. Park, Laurent Bontoux, David Jenkins,

and Robert E. Selleck
and unsaturated
soils lationshipsbetweenKocand organic
pipes (0.75 in.) buriedin bothwater-saturated
Polybutylene
withtoluene,
ando-chlorophenolchemicalaqueous solubility
contaminated
(S, givenin
1,2-dichlorobenzene,
trichloroethylene,
todetectable
levelsin 1 to 150 days,depending
ontheorganic
werepermeated
chemical milligrams
perlitre)oroctanolwaterparanditsconcentration.
oftheseresultswithpipe-bottle
contain- titioncoefficient
(Kow):
Comparison
experiments
oforganicchemical
in thesoilporecontrols
ingno soilshowedthattheconcentration
=
3.95
(1)
logAoc -0.62logS
therateoforganicchemicalpermeation
buriedplasticpipes.Theresultsalso
through
identical
indicate
thatunderotherwise
conditions,
plasticpipesburiedin a soilofhigh
=0.088
+0.909
w
logKoc
logK0
(2)
willbe permeated
moreslowlythanpipeburiedin a soil oflow
organiccarboncontent
Hassettet al indicatedthata good aporganiccarboncontent.Evenso, soils ofveryhighorganiccarboncontentcannotbe
oforganicchemicalsorption
reliedon to protect
A methodfor proximation
plasticpipefrompermeation
byorganicchemicals.
theequilibrium
concentration
oforganicchemical
inthesoilporewasuseful by soils couldbe madefromS and sugpredicting
fromEq
in determining
whethera plasticpipe buriedin contaminated
soil is likelyto be gestedthatKoccanbe predicted
1 witha 95 percentconfidence
levelthat
permeated.
the experimentally
measuredKocvalue
con- willbe within0.90 log units(i.e., less
Duringthelastdecade,waterin some less thanhalfitsaqueoussaturation
whicheveris the controlling thanone orderofmagnitude)
ofthepreplasticandgasketedpipingsystemshas centration,
beencontaminated
Above these levels, the iso- dictedvalue.The 95 percentconfidence
byorganicchemicals factor.4
ofKocfromK0wis
permeating
throughthepipes.The rate thermsusuallybecomeconvexwithre- limitfortheprediction
andextentofpermeation
is thought
tobe spect to the ordinate,indicating
an in- 0.76log units.Othersimilarequations
influenced
Kochavebeensummarized
by varioussoil constituents,creasedsorption
capacityathighorganic forpredicting
inreference
5.
especially organic matter,which can chemicalconcentrations.
sorborganicchemicalsandreducetheir
the
The organicmatter
content
ofdifferent
Kpcanbe calculatedbymultiplying
In this study, soil organiccarbon-organicchemical soilsvariesgreatly:
soil-poreconcentrations.
prairiegrasslandsurofor- partition
coefficient
sorptionexperiments
(Koc
) bytheorganic face soil contains5 to 6 percent,sandy
competitive
ofthesoil (oc). Hassettet desertsoil contains1 percent,and peat
ganicchemicalsbysoilsandplasticpipes carboncontent
wereconductedto investigate
theeffect al3 reducedthe extensiveexperimental soils containmorethan90 percent.6
A
ofsoils on organicchemicalpermeation dataofothersto obtainthefollowing
re- soil'sorganiccarboncontent
can be estithroughplasticpipes and to developa
methodto assess thepotential
ofan orTABLE 1
ganicchemicalcontainedina soiltoperchemicals
usedinsoil-pipe
interaction
studies
Organic
meatea plasticpipe.Compost,a material
witha highorganicmattercontent,
was
Chemical
S (mg/L
Classf
Kow*
Organic
)
Mobility
also used in theseexperiments
to determinewhether
itcouldbe addedtoplastic 0-Chlorophenol
62
28,500
Very
high
pipebeddingtoprotectthepipebysorb- Trichloroethylene
334
Medium
1,100
Toluene
515
522
Medium
ingorganicchemicals.
148
Low
1,2-Dichlorobenzene
2,900
Previousinvestigations
*Octanol-water
from
coefficients
reference
15
partition
Previousworkhas shownthatsoils
interms
ofpotential
from
Griffin
andRoy2)
fClassified
mobility
(adapted
sorborganicchemicals,decreasingtheir
These studies
mobilityand activity.1-4
TABLE 2
have also shownthatthe amountof orResults
andorganic
carbon
ofparticle-size
analysis
ganicchemicalthatcan be sorbedby a
i
i
water-saturated
soil can be predictedby
Carbon
Classification
Organic
byParticle-Size
model(witha
usinga simplepartitioning
Soil
ofdry
percent
Analysis21
weight
partitioncoefficient,
Kp) if the organic
3.9
loam
Clay
carboncontentof a soil, mass of soil, CAD
1.6
loam
Clay
mass ofwater,and mass and typeofor- RFS
CFSL
0.8
Fine
loam
sandy
chemical
are
known.
This
ganic
0.1
sand
simple Sand
Loamy
48
model holds forhydrophobicorganic Compost
chemicalsifthe aqueous-phaseequilibriumconcentration
is below10~5M oris
NOVEMBER
1991

M.HOLSEN
THOMAS
ETAL85

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matedbymultiplying
theorganicmatter
contentby0.59.7
Recentworkon the fateof organic
chemicalvaporsin soil has shownthat
waterandorganicchemicalscompetefor
sitesonmineralsurfaces.
These
sorption
resultsagreedwiththoseofearlierworkers8"12
whofoundthatas therelativehumiditiesin thesoil poresincreased,the
amountoforganicchemicalvaporsorbed
decreased.Atrelative
humidities
greater
than50 percent,the isotherms
became
linear(as theydo in aqueous
practically
solutions),indicatingthatpartitioning
intothesoilorganicmatter
becamemore
thanadsorption
ontotheminimportant
eralsurfaces.
Atabout90 percenthumidity,the amount of organic chemical
sorbedbysoilswas foundtobe equal to
theamountsorbedundersaturated
conditions.
These resultsindicatethatEqs 1
and 2 can be used underunsaturated
as
well as saturatedconditionsifthe soilis high,as is typiporerelativehumidity
cal belowthefirst
fewcentimetres
ofthe
soilsurface.13'14
Materialand methods
The organicchemicalsused in these
are listedin Table 1. Care
experiments
was takento ensurecoverageofa wide
range of soil sorptioncharacteristics.
Chemicalswere all pesticide-grade
and
wereused as received.
ThefoursoilsselectedwereCalifornia
alluvialdeposit(CAD), Richmond
Field
Stationtop soil (RFS), Columbiafine
sandyloam (CFSL), and sand.Compost
was obtainedfromtheEast Bay Municipal UtilityDistrict,Oakland,Calif.Soil
organiccarboncontentsand classificationbyparticle-size
analysisareshownin
Table 2.15The compostparticle-size
distribution
was not determinedbecause
the wide rangeof particlesizes (some
wereup to 2 cmlong)andthedensityof
thecompost(less thanwater)madethe
sedimentation
techniqueinapplicable.
The 1.9-cmID polybutylene
(0.75-in.-)
(PB) pipewas boughtfroma local supplierandwas used as received.
Competitive
sorptionexperiments
All experiments
Saturatedconditions.
wereconductedat20-22C.Six 20.3-cm(8-in.-)diameter,25.4-cm-(10-in.-)long
chloride(PVC) columnswere
polyvinyl
fitted
withclearPVCcoversatbothends,
and twoPB pipes wereplaced through
the columnand its covers.The covers
and pipesweresealed in place withsilicone caulking.The ends of the pipes
weresealed withan aluminum
plugand
silicone caulking.The aluminumplug
had a samplingportcontaining
a PTFEcoatedseptumthrough
whicha 7.6-cmneedlecouldbe
(3-in.-)longhypodermic
introduced
to samplethepipewater.
The columnswerefilledwithsoil and
saturated
withwater.The PB pipeswere
filledwithdistilled
water.Organicchem-

TABLE 3
- saturated
addedtorotating
test
columns
soiltests
Quantities
ofmaterials
SoilType

Chemical
Organic

CAD
RFS
CFSL
Sand
Sand
pluscompost
RFS
Sand
Sand
pluscompost
RFS
Sand
Sand
pluscompost
RFS
Sand
Sand
pluscompost

Chemical
Volume SoilMass Water
Volume
mL
L
kg

Toluene
Toluene
Toluene
Toluene
Toluene
1,2-Dichlorobenzene
1,2-Dichlorobenzene
1,2-Dichlorobenzene
Trichloroethylene
Trichloroethylene
Trichloroethylene
0-Chlorophenol
0-Chloro
phenol
0-Chlorophenol

3.6
3.6
3.6
1.2
1.2
2.2
2.2
2.2
5.0
5.0
5.0
50
50
50

5.3
5.8
5.4
7.3
5.6+0.5
4.8
6.8
5.5+0.5
4.9
7.0
5.7+0.6
5.2
7.1
6.0+0.6

3.0
2.9
3.2
2.7
2.9
3.3
2.8
2.8
3.1
2.8
2.8
2.8
2.8
2.5

TABLE 4
andmeasured
initial
concentration
ofpredicted
Comparison
soil-pore-water
inthesaturated
soilcolumns
Concentration
Chemical
Organic

Soil

Toluene
CAD
Toluene
CFSL
Toluene
RFS
Toluene
Sand
Toluene
Sand
plus
compost
RFS
1,2-Dichlorobenzene
Sand
1,2-Dichlorobenzene
Sand
1,2-Dichlorobenzene
plus
compost
Trichloroethylene RFS
Trichloroethylene Sand
Trichloroethylene Sand
plus
compost
0-Chlorophenol RFS
0-Chlorophenol Sand
0-Chloro
Sand
phenol
plus
compost

From
From
Measured Isotherm Eq 1
mg/L
mg/L mg/L
75
55
74
210
210
182
230
300
197
135
250
260
62
50
18
48
50
45
90
110
47
37
27
35
250
650
540
350
850
1,100
325
380
200
11,300
12,000
24,500
22,200
21,500
28,500
9,600
8,300
9,040

From
Eq 2
mg/L
38
94
100
140
9.4
5.6
11
8.1
260
750
96
7,200
9,100
2,700

300
Toluene
mL
onday
0
added
- 3.5
A-ACAD
water
pore
water
- RFS
mL
0.5
toluene
added
pore
_
250
CFSL
I
water
pore

W
0.5mL
toluene
added

co
O
c

A
50H
0

1-

i
10

'
20

1-

1i
i
i
30
40
50
ofExperiment
Day

=202C
Temperature

i
i
60
70

oftolueneinsoilporewaterinthreecolumnsduring
1. Concentrations
saturated
Figure
sorption
experiments
competitive

86 RESEARCH
ANDTECHNOLOGY

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icalswereinjectedintothesaturated
soil
to startthe experiments
(Table 3) . The
columnswererotatedcontinuously
and
-I
250
Toluene
organic chemical concentrationwas
A ACAD
water
in thesoilporewaterandthe
monitored
pore
water
- T RFS
pore
water.
200
pipe

CFSL
water
pore
^
Unsaturated
conditions.
Soilwas placed
f "
into 15-Lglass bottles,and waterwas
added to bringthewatercontentofthe
- well
soil to approximately
10 percent
O100
abovethewatercontent
ofthesoilsequilibratedwitha relativehumidity
>98 percent.15
The organicchemicalwas added,
the tops of the bottlessealed witha
=202C
Temperature
PTFE-coatedrubberstopper,and the
*
* i- * 1 * i * ' *1
0 I
bottlerotatedon a rollertablefor48 h to
1
60
70 equilibrate
0
10
20
30
40
50
thesoilandtheorganicchemofExperiment
Day
icalvapor.
The soil was thenremovedfromthe
oftolueneinPB pipewaterinthreecolumnsduringsatFigure2. Concentrations
uratedcompetitive
glass bottlesand packedintoPVC colexperiments
sorption
umnsthroughwhichtwo 1.9-cm(0.75in.) PB pipes had been placed. The
amountof organicchemicalsorbedon
200
thesoilwas determined
atthestartofthe
0.5mL
toluene
added
experiments
byplacingsoilsamplesinto
Toluene
- w X
175
1.2mL
0
toluene
added
onday
centrifugetubes and extractingthem
"_ ^
Sand
water
pore
with
5 mL of a mixtureof 50 percent
A-ASand
+compost
water
7Y J T
0.5mL
toluene
added
pore
hexaneand50 percentre/'
/
I
X
Sand
water

reagent-grade
pipe
150
A-ASand
+compost
water
pipe
y /
/ ' / 1
agent-gradeacetone. The vials were
mixedbyrotating
themfora minimum
of
4 h and thenwerecentrifuged.
The organic chemicalmixturewas thenana(GC).
lyzedbya gas chromatograph
At the end of the experiment,the
amountof organicchemicalin the soil
was again determined
usingthe procedure just described.The experiments
wereconductedat 20 2C.
Organicchemicalanalysis.A GC,* a
sample concentrator
equippedwithan
25
=202C
JOT
Temperature
autosampler(purgeand trap),fand a
headspacegas analyzer^wereused for
- f-ao- Dmq | - Dq Din
1
all requiredanalyses.
| a-,
10
40
50
60
70
0
20
30
Liquid sampleswere analyzedby diof
DayExperiment
rectinjection
whentheirconcentrations
oftoluenein porewaterand PB pipewaterin a sand
were greaterthan approximately
0.5
Figure3. Concentrations
andsandpluscompostcolumnduringsaturated
competitive
sorption
experiments mg/L,dependingon theorganicchemical involved.Sampleswere introduced
intoa 2-m-long,
2-mm-IDpacked glass
-1
column.
300
Liquidsampleswitha concenToluene
trationof less than approximately
0.5
water
O- OCAD
pore
A- ACFSL
water
pore
mg/Lwere analyzedusingthe sample
^E250
~
RFS
water
pore
concentrator
inconjunction
withtheGC.
"
A___.
ofthesample
Operationand calibration
concentrator
followed
US Environmental
0-93
2.200
Protection
methods601 or 602,
Agency
0.98
C
1/
o II
dependingon theorganicchemical.16,17
=202C
I
Temperature
150
Vapor sampleswere analyzedusing
the headspace analyzerin conjunction
I
0
1
withtheGC. The entiresystemwas cali0'50
I100"
bratedby analyzingthe headspacegas
abovewatercontaining
a knownconcenP
1 sotration
oforganicchemical.
^
Decimals
indicate
initial
relative
concentrationThe concentration
oforganicchemical
o--"C
1
,rT
1
1
1
1
1
1
1
0-cjM== 1
in soil poreswas determined
byplacing
10
40
50 saturatedsoil
0
20
30
into
2-mL
reactor
samples
of
DayExperiment
ofconcentrations
oftoluenein thePB pipewaterofCAD,
Figure4. Comparison
*Model
Pa.
5880,
Hewlett-Packard,
Avondale,
-soilcolumns
O.I.Corp.,
Texas
RFS,andCFSL unsaturated
4460,
fModel
Station,
College
Pa.
19395A,
JModel
Hewlett-Packard,
Avondale,
B/3%
SP-1000,
80/120
Carbopack
Inc.,
Supelco
Pa.
I Bellafonte,
NOVEMBER
1991

THOMAS
M.HOLSENETAL
87

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sand and
thatin thecolumncontaining
compost(Figure3) . Thisalloweda much
fastertoluenebreakthrough
(about 25
versus50 days).The greatertolueneupinthe
takeas a resultofpipepermeation
mgsorbed
From From From
sand columncaused a more rapiddeper1,000
Chemical
Soil
g soil MeasuredIsothermEq 1 Eq 2
Organic
inthe
creaseinthetolueneconcentration
water
in
this
column
following
soil-pore
0.50
0.5
0.82 0.42
Toluene
CAD
3,040
thefinaladditionoftolueneon day19.
1.0
1.0
1.0
0.93
Toluene
CFSL
3,560
1.0
1.0
1.0
0.98
Toluene
RFS
4,000
Experiments similar to those de1.0
1.0
1.0
950
0.92
Toluene
Sand
scribedwerecarriedoutusingcolumns
0.7
0.63 0.32
0.70
Sand
Toluene
compost 2,400
plus
1.9-cm(0.75-in)PB pipesand
containing
0.64 0.51 0.24
0.68
RFS
1,000
Trichloroethylene
RFS soil,CFSL soil,sand,anda mixture
0.78
1.0
1.0
725
0.83
Sand
Trichloroethylene
0.81
0.85 0.23 0.11
Sand
Trichloroethylene
plus
compost 1,400
of sand and compostand the organic
0.58 1.0
0.32
0.50
7,300
0-ChlorophenolRFS
trichlochemicals1,2-dichlorobenzene,
1.0
1.0
0.93
1.0
Sand
3,160
o-Chlorophenol
Results
and
0-chloro
phenol.
roethylene,
0.44
0.53
0.26
0.1
Sand
plus
compost 5,100
o-Chlorophenol
- theconweresimilartothosereported
in the
chemicals
centration
of
organic
300
|
waterdecreasedwithincreassoil-pore
Toluene
^
inthesoiland
ingorganiccarboncontent
O-OSand
f250- ASand
timesincreased.
A
plus
compost
apparentbreakthrough
jj
of
The predictedinitialconcentration
O^o0.92
| g.200
water
f
organicchemicalsin thesoil-pore
a.
/
/
c
foreach soilwas comparedwiththeex0) /
/
g150
measuredvalue usingthe
perimentally
"
0.70
codetermined
I
partition
experimentally
=202C
*5
/
Temperature
100efficients15
betweenthesoilandwaterfor
/
/
o
a particular
organicchemicalandvalues
fromsolubility
(Eq 1) andK0w
predicted
c 50- A
/
/
(Eq 2), the initialsoil mass, the initial
initial
relative
Decimals
indicate
concentration
watermass,andtheinitialamountofor1
A|A *i
1
1
1
1
1
1
1
1
1
1
ganicchemicalinjectedbymassbalance.
20
50
60
0
10
30
40
ofExperiment
As shownin Table 4, measuredconDay
in the
centrationsof trichloroethylene
in
PB
from
a
sand
and
of
toluene
concentrations
water
5.
Figure Comparison
pipe
than
water
were
lower
presoil-pore
column
sandpluscompostunsaturated-soil
dictedfromthe isothermsforall soils,
sandand RFS soil,probably
particularly
vessels sealed withPTFE-coatedsepta content(3.9 percent),andhighestinthe as a resultoftherapiduptakeoftrichloat CFSL soil column,whichhad thelowest roethylene
and screwcaps and thencentrifuged
by the PB pipes (thevalues
determinedexperimentallywere ob5,000rpmfor30 min.The supernatant organiccarboncontent(0.8 percent).
wasthenanalyzedinthesamemanneras
Figure2 showsthatthesoil-pore-watertainedonedayafterorganicchemicaladhad a markedef- dition)
. Evenso,thereis a fairagreement
tolueneconcentration
thepipewatersamples.
intothe betweenpredictedand measuredinitial
fectonthetoluenebreakthrough
Results
of toluene,1,2-dichloropipewater.In theCFSL soil,whichhad concentrations
in thesoilof toluenein benzene,and 0-chlorophenol
of organicchemi- the highestconcentration
Competitive
sorption
oc- pore water.Differencesbetweenprecals bysoils and plasticpipes. Results the soil-porewater,breakthrough
14 days; in dicted and experimentalvalues were
inwhichtwo curredafterapproximately
froma duplicateexperiment
in
identicalcolumnswere contaminated theRFS soil,whichhad an intermediateprobablyalso because of differences
oftoluenein thesoil-pore soil preparation
betweenthe isotherm
withtolueneshowedthatsoil-poretolu- concentration
occurredafterap- studies and the columnexperiments.
weresimilar
eneconcentrations
through- water,breakthrough
16 days; in the CAD soil, Soils used in the isothermswere careout the 45-dayexperiment.
Pipe-water proximately
of fullysievedto removemostoftheroots,
in bothcolumns whichhad the lowestconcentration
tolueneconcentrations
and in twopipescontainedin the same toluene in the soil-porewater,break- debris,and pebbles,whereas the soil
wasonly
didnotoccuruntilafter50 days. usedinthecolumnexperiments
These re- through
columnwerealmostidentical.
A similarexperiment
was carriedout roughlycleaned of larger rocks and
are
sultsindicatethatthe experiments
and thatthe toluenecon- witha 1.9-cm(0.75-in.)PB pipeinwater- clumpsofroots.
reproducible
centrationswere uniformthroughout saturatedsand (a popularpipe-bedding Predictions
usingEqs 1 and 2 are in
sand to fairly
withmeasuredvaleach column.
material)and water-saturated
goodagreement
PB pipes [1.9-cm(0.75-in.)]were ex- which approximately10 percent by ues exceptwhensandandcompostwere
is notsurprisThisdiscrepancy
posed to toluenein separatecolumns weightcomposthad been added. The involved.
was todetermine ing because the predictiveequations
containingCAD, RFS, and CFSL soils. goal ofthisexperiment
Soils were added to the columns,and whethercompostcouldbe added to in- weredevelopedforsoil,notcompost.In
fromsolubility
aftersaturation
withwater,3.6 mL tolu- crease the amountof organicchemical general,predictions
(Eq
some degree 1) appearto be betterthanthosefrom
ene was added. On days8 and 19,addi- sorbed,therebyaffording
bothequationsgive
tionaltoluene(0.5mL)wasaddedtoeach of protectionagainstpermeation.Ini- ifow
(Eq 2); however,
columnto maintainthe soil-pore-watertially,1.2mLtoluenewas added;an addi- good firstestimatesof the equilibrium
water.
inthesoil-pore
tolueneconcentration
(Figure1). With tional aliquot of 0.5 mL toluene was concentrations
Unsaturated
thesamemassoftolueneineachcolumn, addedon days3, 8, and 19.
experisorption
competitive
exthesoil-pore-water
tolueneconcentration In the columncontainingsand only, ments.An unsaturated-soil-column
oftoluenein thesoil- perimentwas conductedto determine
was lowest in the CAD soil column, the concentration
oforganic
distribution
a uniform
muchhigherthan whether
whichhad the highestorganiccarbon porewaterwasinitially
TABLE 5
initial
concentrations
andmeasured
relative
ofpredicted
Comparison
inunsaturated-soil-column
experiments

ANDTECHNOLOGY
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-|
chemicalon thesoilwas beingachieved.
~S 100
Toluene
>
of toluenein the pipe
Concentrations
OBottle
experiments
8. "

ASaturated-soil-column
experiments
intwopipesplaced
waterweremonitored
~
75

Unsaturated-soil-column
experiments
2
in
inRFS soil.The tolueneconcentration
2c
water in the two pipes was similar
cJ
A
AO
1*f 50theexperiment.
throughout
o
soil-column
Unsaturated
&o
experimental m
u
=202C
Temperature
g 25o=
resultson CAD, RFS, and CFSL soils
A
A

^
of
these
soils
for
all
show
that
(Figure4)

the same
(whichsorbedapproximately
1
oI 0-|
1
1
1
i
1
1
1
1
1
amountof toluene, Table 5) toluene
1.0
0.8
0.6
0.4
0.2
0.0
was much fasterin the
breakthrough
Relative
Concentration
RFSandCFSL soilsthanintheCAD soil.
of 1
to reacha tolueneconcentration
time
needed
of
the
6.
Figure Comparison
time
in breakthrough
These differences
exthe
unsaturated-soil
and
for
the
water
in
the
saturated-soil,
bottle,
pipe
mg/L
were a resultof the different
soil-poreThe rela- periments
vaportolueneconcentrations.
75- 1
oftoluenein the soil
tiveconcentration
o
c
0
pore in equilibriumwiththe soil was
1 60foundtobe 0.53fortheCAD soil,0.98for
Trichloroethylene
g
theRFS soil,and 0.93 fortheCFSL soil
2
OBottle
experiments
g
0
ASaturated-soil-column
experiments
in
(Table 5). These resultsare reflected
45unsaturated-soil-column
o.
experiments
Figure4, whichshows thatthe fastest a
22
concentration
andhighest
breakthrough
2 c 30oftoluenein thepipewaterare foundin
O
1E
conthesoilwiththehighestpore-vapor
=202C
Temperature
These resultsare consistent . 15centration.
A

a
much
A
withthefactthattheCAD soilhas
o

S
A
n- 1
higherorganiccarboncontentthanei1

'

1
1
1
1
H
thertheRFS or CFSL soils.
1.0
0.8
0.6
0.4
0.2
o.o
The resultsofunsaturated-soil-column
Concentration
Relative
experimentson tolueneand sand and
concentraofthetimeneededtoreacha trichloroethylene
sandpluscompostindicatedthattoluene
Figure7. Comparison
and theunsatutionof 1 mg/Lin thepipewaterforthebottle,saturated-soil,
was much fasterin the
breakthrough
rated-soil
sandthaninthesandpluscomposteven
experiments
200thoughthesandpluscompostcontained

1,2-Dichlorobenzene
^a
2.5 timesmore toluene
>
OBottle
approximately
experiments
8.
A
Saturated-soil-column

experiments
thanthesand (Figure5). Again,thisre150
8E
a>

the
cc
sultcan be explainedby comparing
o
c
inthesoil
relativetolueneconcentration
measured
A
by headspaceanalysis.
pores
J|100o
thisvaluewas
Forthesandpluscompost,
|i
iEc
=202C
Temperature
A
0.7;forthesandalone,itwas 0.92.
5| 50The resultsofunsaturated-soil-column QC "
O
8
and oon trichloroethylene
experiments
i
i
1
1
3
1
|
|
1
1
1
o-|
chlorophenoland RFS soil, sand, and
1.0
0.8
0.6
0.4
0.2
0.0
sand plus compostwereverysimilarto
Concentration
Relative
thosedescribedearlier.The soilwiththe
conofthetimeneededto reacha 1,2-dichlorobenzene
Figure8. Comparison
(sand)
highestpore-gasconcentration
experiof 1 mg/Lin thepipewaterforthebottleand saturated-soil
permeatedthe PB pipes most rapidly, centration
ments
andthesoilwiththelowestpore-gascon300-1
centration
(RFS) yieldedthelowestperof the actual
o-Chlorophenol
meationrate irrespective

OBottle
experiments
_
mass oforganicchemicalpresentin the
2g0
ASaturated-soil-column
.2
experiments
column.
2
Unsaturated-soil-column
experiments
Unsaturated-soil-column
experiments 0 0
200

g
were unsuccessfulwith 1,2-dichloro- o
o

benzene because (1) the 1,2-dichlorotimewas greater If

benzenebreakthrough
A
a O
{'"
concentration
than20 daysatrelative
0.8,
o
O
A
EE
(2) the mass of 1,2-dichlorobenzene !|l00sorbedby soils was onlyapproximately 8.^
a
1,250mg/l,000gforRFSsoil,and(3) the
50A
coefficient 1
1,2-dichlorobenzene
partition

=202C
Temperature
withPB was veryhigh (approximately
18
25,000at activity
0.70). For theserea.
1
.
i
1
1
1
1
1
o-|
1
of 1,2-dichlorosons, the concentration
1.0
0.6
0.8
0.2
0.4
0.0
Relative
Concentration
benzenein the soil-poregas in the columns dropped rapidly during the
concentraofthetimeneededto reachan 0-chlorophenol
Figure9. Comparison
and the PB pipeswerenot
experiment,
and theunsatutionof 10 mg/Lin thepipewaterforthebottle,saturated-soil,
permeatedto a detectabledegreeeven
rated-soil
experiments
after50 days.
M.HOLSENETAL
89
THOMAS

NOVEMBER
1991

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All use subject to JSTOR Terms and Conditions

Measuredand predictedrelativeconThe resultsoftheseexperiments

indi- thanthe diffusion
coefficients
through
centrations
forthe entirerange of or- cate thatthe concentration
of organic the plasticpipe wall;however,because
ganicchemicalsandsoils (Table5) show chemicalin the soil pore controlsthe theconcentration
gradientin theplastic
excellentagreementexceptforexperi- permeationrate and thatthe soil-pore may be several orders of magnitude
mentsin whichcompostwas used.The concentration
can be predicted
fromex- greaterthanin the soil,18thereis the
concentration
oforganicchem- perimentally
determined
or empirically possibility
ofexternal-phase
predicted
mass transical in thevaporphase was obtainedby predictedpartition
coefficients
between ferlimitations,
in saturated
particularly
theamountoforganicchemical thesoilandwaterfora particular
dividing
organic soil. However,soil-porewaterand soilsorbed (mg/1,000g soil) by its experi- chemicaliftheinitialsoilmass,theinitial pore gases are constantlymovingbedetermined
coefficientwatermass,and the amountoforganic cause ofpressuregradientsandgravity,
mentally
partition
or partitioncoefficients
obtainedfrom chemicalare known.The experimental whichwillhinderthe development
ofa
Eqs 1 and 2. These resultsmustthenbe resultsalso indicatethatpipesburiedin boundary
layer.
dividedbytheaqueous solubility
ofthe soils highin organiccarboncontentor
events
organicchemical(inmilligrams
perlitre) thattheuse ofcomposttoincreasea soil Analysisofpotentialpermeation
to obtaina relativeconcentration.
These experimentalresults can be
organiccarbon contentincreasedthe
Thetimesrequiredtoreachconcentra- timerequiredtoorganicchemicalbreak- used to developa methodto assess the
tionsof1 mg/L,1 mg/L,1 mg/L,and 10 throughcomparedwithpipesburiedin potential
ofa soiltoinfluence
thepermefortoluene,trichlo- soilslowinorganiccarboncontent;
how- ationofplasticpipesby organicchemimg/L,respectively,
and o- ever,innoneoftheexperiments
wasper- cals. It has been shownthattherelative
1,2-dichlorobenzene,
roethylene,
inthepipewaterforunsat- meationeliminated.
in the
chlorophenol
organicchemicalconcentration
uratedsoilsarecomparedwiththetimes
soil pores controlsthe rate of permealimitations
tion.Therefore,
thesoilmustbe analyzed
requiredforsaturatedsoil and pipe-bot- Mass transfer
tleexperiments18
inFigures6-9.
The possibility
ofmasstransfer
limita- insucha waythattherelativeconcentraThe graphsare plottedintermsofthe tionsbetweenthephase externalto the tionoforganicchemicalinthesoilpores
toreacha pipe-wa- pipeandtheplasticpipewallitselfmust can be predicted.
dayoftheexperiment
terconcentration
of1 or 10mg/Lversus be consideredbeforesaturated-soil-col- In ordertoaccomplish
this,twothings
external
wateror soil-pore
waterrelative umnresultsare appliedto actualperme- mustbe known:theamountofchemical
concentration
so thatthe experimental ationeventsbecausethesecolumnswere sorbedon thesoil and thesoil'sorganic
resultscan be comparedeven though mixed. Mass transferlimitationscan carboncontent.The amountoforganic
theywere not runat exactlythe same occurwhenorganicchemicalabsorption chemicalsorbedonthesoilcanbe deterexternalrelativeconcentrations.
The re- by the pipe wall is fastenoughto de- mined eitherby purge-and-trap
techsults of the two typesof experiments crease theexternalconcentration
ofor- niquesin whicha knownamountofsoil
agreeverywelleventhoughtheexperi- ganicchemicalimmediately
adjacentto is placedina glassvessel,andthesorbed
mentsdiffered
as follows:(1) organic thepipewall.Thisdecreaseinconcentra- organicchemicalis stripped
fromthesoil
chemicalswereadded to thepipe-bottle tionwouldoccuriftheorganicchemical withan inertgas and introduced
intoa
severaltimeseach weekto fluxintothe pipe wall is similarto or GC forquantification.
experiments
a
Alternatively,
keep the externalconcentration
fairly larger than the movementof organic knownamountof soil can be extracted
so theexternalorganicchemi- chemicalup to thepipewall.The bound- witha knownamountofsuitablesolvent
constant,
cal concentration
in the pipe-bottle
ex- arylayercreatedbythisdecreasein ex- (e.g., 1:1 hexane:acetone),the mixture
fluctuated
a greatdeal more ternalorganicchemicalconcentration centrifuged,
and the supernatantanaperiments
thaninthesoil-column
and wouldincreasethe amountof timere- lyzedchromatographically.
experiments,
ofthepipe-bottle
ex- quiredforan organicchemicaltoperme- The organiccarboncontent
(2) thetemperature
ofthesoils
was morecloselycontrolled ate a plasticpipebecausethepipewould can be determined
periments
usingthe modified
thaninthesoil-column
be exposedto a concentration
less than Mebius procedure.20
Once the organic
experiments.
For 1,2-dichlorobenzene,
carboncontent
ofthesoilandtheamount
toluene,and thatseeninthebulkexternalphase.
thetimethatwas reThe fluxofanorganicchemicalis char- oforganicchemicalsorbedbythesoilis
trichloroethylene,
itsdiffusion
co- known,theKocforeach chemicalcan be
quiredtoreach1 mg/Linthepipewater, acterizedbymultiplying
at the same externalrelativeconcentra- efficient
byitsconcentration
gradientin calculatedfrom
Eq 1 or2 ortheequations
5.
tion,was thesame regardlessoftheex- the media of interest.Because plastic in reference
ternalphase.
The partition
coefficient
betweenthe
pipesare buriedin soil inwhichthesoil
A comparisonof the timethatwas poresare filledwitheitherwateror air, organicchemicaland the soil, Kp,can
needed in orderto reach a pipe-water diffusion
coefficients
of organicchemi- thenbe calculatedbymultiplying
Kocby
concentration
of10mg/Lo-chloro
bothsaturatedand unsatu- oc. The concentrationof the organic
phenol cals through
forthepipe-bottle
and soil- ratedsoilsmustbe considered.
Soilsgen- chemicalintheporespace (Cp)canthen
experiments
column experimentsconductedwith erallydecrease air or waterdiffusion be predictedby dividingthe amountof
PB pipe(Figure9) showsthatthe coefficients
0.75-in.
byone ortwoordersofmag- organic chemical sorbed on the soil
saturatedsoil resultsdo notagreewith nitude,primarilybecause of the de- (mg/1,000g soil) by Kp. The organic
the unsaturated
soil resultsor thepipe- creased area availablefordiffusion
and chemicalporespace relativeconcentrabottleresults,particularly
atrelative
con- the tortuouspath that the chemicals tioncan thenbe determined
bydividing
centrations
above0.2.Thislackofagree- must follow. Diffusioncoefficients Cpbytheorganicchemicalaqueous solmentmay have been caused by poor through
waterare on theorder ubility
inmilligrams
stagnant
perlitre.
ex- of 10" cm2/s,and diffusion
coefficients For example,considera soil withan
mixingin the saturated-soil-column
Ten timesas muchorganic throughstagnant
airare on theorderof organiccarboncontentof2 percentand
periments.
chemicalwas added to the0-chlorophe-10"1cm2/s.9 Thus, forsaturatedsoils, a sorbed tolueneconcentration
of 863
nolcolumns(50mL)as toanyoftheother diffusion
coefficients
willbe ontheorder mg/1,000
g soil.BecauseKocfortoluene
soil columns.This may have allowed of 10"6cm2/sand forunsaturated
withEq 1) Kpis 186
soils, is 186 (determined
smallpocketsofessentially
co- x 0.02= 3.7,andCpis 863/3.7= 232mg/L.
pure0-chlo- on theorderof10"2cm2/s.Diffusion
PB andPE pipeare on The relativeconcentration
oftoluenein
rophenolto be in contactwiththepipes efficients
through
thesoilporesis 232/515= 0.45(515is the
duringthe initialstages of the experi- theorderof10" cm2/s.18
ina muchfaster0-chloro- The diffusion
coefficients
soil aqueous solubilityof toluenein milliment,resulting
through
are severalordersof magnitudelarger gramsper litre).If it is assumedthat
phenolbreakthrough.
90 RESEARCH
ANDTECHNOLOGY

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AWWA
JOURNAL

II.TheSorption
relativeconcentration
and activityare tion. At equivalent relative concen- 9. Wade,P. SoilFumigation
Dibromide
OfEthylene
bySoilsat Low
thisvaluecanthenbe usedto tration,the pipes were permeatedthe
equivalent,
WaterContents.
Sci.FoodAgr.,6:1
Jour.
followed
makepredictions
aboutthetimeneeded fastestbytrichloro
ethylene,
by
and0-chlo- 10. (1955).
to reach detectablelevels of toluenein toluene,1,2-dichlorobenzene,
IV.Sorption
of
Call, F. SoilFumigation
the pipe usingtechniquesdescribedin rophenol.Comparisonof these soil-colDibromide
onSoilsatFieldCaEthylene
umnresultswithpipe-bottle
Parket al18or Figures6-9.
experiments
Sci.FoodAgr.,
8:137(1957).
pacity.
Jour.
no soil indicatethatthecon- 11. Spencer,
This calculationassumesthatthepar- containing
W.F.& Cliath,
M.M.Desorption
oforganicchemicalinthesoil
tition
coefficient
ofLindane
from
Soilas Related
toVapor
Kpis linearatall relative centration
SoilSci.Soc.Amer.,
34:574
butin actuality
itgener- pore space controlsboth the rate and
Density.
Jour.
concentrations,
(1970).
at relativecon- extentof organicchemicalpermeation
allyincreasesnonlinearly
W.F.;Cliath,M.M.;& Farmer,
>0.5. At relativeconcentra- through
buriedplasticpipes.The results 12. Spencer,
centrations
ofSoil-Applied
DielW.J.
Vapor
Density
identitions >0.5, this methodwould tend to also indicatethatunderotherwise
drinas Relatedto Soil-Water
Content,
in
buried
soil
the organicchemicalrela- cal conditions,
overestimate
plasticpipes
andDieldrin
Concentration.
Temperature,
tiveconcentration,
makingita conserva- of highorganiccarboncontentwillbe
SoilSci.Soc.Amer.
33:509(1969).
Jour.
is permeatedmoreslowlythana pipebur- 13. Puri,AN.Soils,Their
tiveapproach.This typeofcalculation
andChemisPhysics
also appropriatefororganicchemical ied in a soil oflow organiccarboncontry.ReinholdPubl. Corp.,NewYork
mixtures
at lowrelativeconcentrations. tent.Evenso, soils ofveryhighorganic
(1949).
& Ashcroft,
G.L.Applied
Soil
R.J.
carboncontentcannotbe reliedon to 14. Hanks,
Effects
ofbackfill
New
York
Springer-Verlag,
typeon permeation protectplasticpipefrompermeation
Physics.
by
Ifproperly
used organicchemicals.The typesof sand 15. (1980).T.M.Effect
designed,thebackfill
ofSoilsonthePermeHolsen,
to surrounda plasticpipecan helplimit commonly
used as backfill
materialthat
ationofPlasticPipesbyOrganic
Chemiits susceptibility
to permeation
by sorb- have bothverylow organiccarbonconcals.Doctoral
Univ.Califordissertation,
afford
ing contaminants,
therebydecreasing tentand veryhigh permeability
nia,Berkeley
(1988).
theirconcentrations,
Protection
and/orphysically littleprotection
againstpipepermeation. 16. US Environmental
Agency.
TestMethod:Purgeable
Halocarbons
contaminant
access to the pipe Thus,sandshouldnotbe usedas backfill
limiting
Method601.Environ.
and
Monitoring
barrier.As forplasticpipesexceptwhereabsolutely
by creatingan impermeable
Ohio.
Lab.,Cincinnati,
Support
showninthiswork,soilsofhighorganic necessary,and, at a minimum,
native
US Environmental
Protection
Agency.
carboncontentor the additionofa soil soils shouldbe used in theirplace be- 17. Test
Method:PurgeableAromatics
withhighorganiccarboncontent
toa soil cause oftheirhigherorganiccarbonconMethod602.Environ.
and
Monitoring
oflow organiccarboncontentcouldbe tentandlowerpermeability.
Ohio.
Lab.,Cincinnati,
Support
used to significantly
increasethe time
18. Park,J.K.et al. PipePermeation
Study,
neededto permeatea pipeand thussig- Acknowledgment
FinalRept.Interagency
No.
Agreement
Between
84/84371
decrease the finalconcentra- This researchwas fundedbytheCaliDept.ofHealthSernificantly
andtheRegents
vices,StateofCalifornia,
inthepipewater. forniaDepartmentof Health Services
tionofthecontaminant
oftheUniv.ofCalifornia,
San.Engrg.
and
of
Alternatively,
fine-grained
compressible andwas conductedbytheDepartment
Envir.
HealthRes.Lab.,Univ.ofCaliforsoils suchas claycouldbe used to limit CivilEngineering
and the Sanitaryand
nia,Berkeley
(1989).
themovement
ofa contaminant
andphys- Environmental
HealthResearchLabora- 19.Thibodeaux,
EnviL.J.Chemo
dynamics:
ofCalifornia
atBerkeley.
icallyprotecta buriedpipefrompermea- tory,
University
ronmental
Movement
inAir,
ofChemicals
tion.Unfortunately,
have
claysgenerally
andSoil.)John
& Sons,New
Water,
Wiley
a verylow organiccarboncontentand References
York(1979).
1. Karickhoff,
S.W.;Brown,
D.S.;& Scott, 20. Nelson,
D.W.& Sommers,
L.E.Methods
thereforelow sorptivecapacity.The
of
T.A.Sorption
ofHydrophobic
Pollutants SoilAnalysis,
Part2: Chemical
andMicroused as backfill
typesofsandcommonly
on
Natural
Sediments.
Water
13:241
Res.,
bialProperties
(A.L.Pageet al,editors).
materialaffordlittleprotectionto the
(1979).
SoilSci.Soc.Amer.
(1982).
pipebecausetheyhaveveryloworganic 2. Griffin,
R.A.& Roy,W.R.Interaction
of 21. Plaster,E.J.Soil Scienceand Managecarboncontentand therefore
verylow
Soil
OrganicSolventsWithSaturated
ment.
Delmar
N.Y.(1985).
Publ.,
Albany,
Water
sorptivecapacityand veryhighpermeSystems.
OpenFileRept.
prepared
fortheEnvironmental
becauseoftheirlargeparticlesize.
Institute
forWaste
ability
ofAlaFor these reasons,sand shouldnot be
Studies,
Management
University
About the authors:
bama,Huntsville
(1985).
used as backfill
ThomasM. Holsenis
exceptwhereabsolutely
Banwart,
W.L.;& Griffin,
native 3. Hassett,J.J.;
an assistantprofessor
necessary,and, at a minimum,
R.A.Correlation
ofCompound
Properties
soils shouldbe used in theirplace bein theEnvironmental
With
Characteristics
ofNonpolar
Sorption
causetheygenerally
havehigherorganic
EngineeringDepartConCompounds
bySoilsandSediments:
carbon contentsand lowerpermeabilment,IllinoisInstitute
Environment
and
ceptsandLimitations.
itiesthansand. It mustbe noted,how3200 S.
SolidWastes
andS.I.AuerofTechnology,
(C.W.Francis
AnnArbor
Sci.Publ.,Ann
StateSt., Chicago,IL
bach,editors).
ever,thatthe use of soils withhighort
Mich.(1983).
Arbor,
60616. A graduateof
ganic carbon content and/or low
S.W.Organic
Pollutant
Sorp- theUniversity
cannotbe used to assure 4. Karickhoff,
with
permeability
of
California,
Berkeley,
tionin AquaticSystems.
. Hydr. BS, MS, and PhD
Jour
ofplasticpipesfrompermeaHolsenis a
protection
degrees,
(1984).
Engrg.ASCE,110:6:707
- theycanonly
tionbyorganicchemicals
member
oflAWPRC,
ACS,andAEEP. His
5. Lyman,
J.W.;
Reehl,W.F.;& Rosenblatt, work
be used to decreasethenumberofperhas
been
fry
Jourpublished
previously
D.H.Handbook
EstiofChemical
Property
meationincidents.
mation
Methods.
Amer.
Chem.
Soc.,Wash- nal AWWAand JournalWPCF.Jae K.
Parkisan assistant
at theUniverD.C. (1990).
professor
ington,
Conclusions
6. Bohn,H.; McNeal,B.; & O'Conner,
G. sityofWisconsin
(Madison),1415Johnson
SoilChemistry.
John
The resultsreported
herehaveshown
Wiley& Sons,New Dr.,Madison,WI53706.LaurentBontoux
York(2nded.,1985).
that0.75-in.
is a research
scientist
withProcter
& Gampolybutylene
pipesburiedin
N.C.TheNature
andProperties
of ble,EuropeanTechnicalCenter,
both water-saturated
and unsaturated 7. Brady,
Temselan
Soils.MacMillanPublishing
Co., New 100 B-1820 Strombeekbever,
soils contaminated
withtoluene,trichloBelgium.
York(8thed.,1974).
and
ois a professor
andRobert
E.
1,2-dichlorobenzene,
roethylene,
8. Chiou,
C.T.& Shoup,
T.D.SoilSorption
of DavidJenkins
werepermeatedto detectemeritus
in theDepartchlorophenol
ofHumiditySelleckisprofessor
Organic
VaporsandEffects
ablelevelsin1 to 150days,depending
on
on Sorptive
Mechanism
and Capacity. mentof CivilEngineering,
of
University
the organicchemicaland its concentraEnvir.
Sci.& Technol.,
19:1196
CA94720.
(1985).
California,
Berkeley,
NOVEMBER
1991

THOMAS
M.HOLSEN
ETAL91

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