Soil and Groundwater Contamination: Nonaqueous Phase Liquids-Principles and Observations

218 Pages·2005·3.604 MB·English

Water ResourcesM onograph 17
SOIL AND GROUNDWATER
CONTAMINATION-
NONAQUEOUS PHASE LIQUIDS-
PRINCIPLES AND OBSERVATIONS
Alex Mayer
S. Majid Hassanizadeh
Editors
R.W. Falta, S. M. Hassanizadeh,
T.H. IllangasekareI,. Javandel,
K. H. JensenA, . S. Mayer, and M. Oostrom
ContributingA uthors
AmericaGne ophysUicnailo n
Washington,D C
Publishedu ndert he aegis of the AGU Books Board
Jean-LouisB ougeret, Chair, Gray E. Bebout, Cari T. F riedrichs, James L. Horwitz,
Lisa A. Levin, W. Berry Lyons,K ennethR . Minschwaner,A ndy Nyblade, Darrell Strobel,
and William R. Young, members.
Mayer, Alex.
Soil and groundwaterc ontamination:n onaqueoups hasel iquids/ Alex Mayer.
p. cm. -- (Water resourcesm onograph;1 7)
Includesb ibliographicarle ferencesa nd index.
1. Oil pollutiono f soils.2 . Oil pollutiono f water.3 . Nonaqueousp hasel iquids--
Environmentala spects4. . Soil remediation5. . Groundwater--PurificationI.. Title.
II. Series.
TD879.P4M353 2005
628.1'6833--dc22
2005006928
ISBN-13:978-0-87590-321-7
ISBN-10: 0-87590-420-3
ISSN 0170-9600
Copyright2 005 by the American GeophysicaUl nion
2000 Florida Avenue, N.W.
WashingtonD, C 20009
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Table of Contents
Preface ........................................................ v
1 Introduction
A. S. Mayer and S. M. Hassanizadeh .............................. 1
2 Fundamentals
K. H. densen and R. tE. Falta ..................................... 5
2.1 NAPL Characteristics and behavior of NAPLs
in the subsurface ....................................... 5
2.2 Parametersr esponsiblefo r NAPL distributiona nd flow
in the subsurface ....................................... 9
2.2.1 Interfacialt ensiona nd wettability .................... 9
2.2.2 Capillaryp ressurea nd capillaryp ressurec urves ....... 12
2.2.3 Relativep ermeabilitya nd relativep ermeability
curves ......................................... 24
2.2.4 Darcy's law and governinge quationsf or
multiphasefl ow ................................. 27
2.3 NAPL masst ransfera ndt ransport ........................ 30
2.3.1 VaporP ressurea nd Solubility ...................... 31
2.3.2 Phase Densities ................................. 32
2.3.3 Concentrations .................................. 34
2.3.4 EquilibriumP haseP artitioning ..................... 37
2.3.5 MultiphaseT ransporMt echanisms. ................. 43
Migration and Distribution
T. H. IllangasekareK, . H. JensenI,. Javandel,a ndA . S. Mayer ..... 47
3.1 Residuala nd trappeds aturations.. ........................ 47
3.2 The role of geologicalh eterogeneity.. ..................... 49
3.3 Interactions with the water table .......................... 54
3.3.1 LNAPL accumulation on water table ................ 54
3.3.2 DNAPL poolingo n vs. penetrationo f the water
table .......................................... 56
3.3.3 Smearingo f LNAPL due to water table fluctuations. ... 59
3.4 Capillaryb arbersa ndc hannels. .......................... 63
3.4.1 NAPL poolingo n vs. penetrationo f low permeable
material ....................................... 63
3.4.2 Migrationo f DNAPLs alongs lopingc onfining
layers ......................................... 72
3.4.3 Occurrenceo f NAPLs in high permeability
regions ........................................ 76
3.5 Small scale NAPL distribution ........................... 81
3.5.1 UnstableF rontsa nd Fingers ....................... 81
3.5.2 Occurrenceo f NAPLs in clay or rock fractures ........ 86
Site Characterization and Monitoring
A. S. Mayer and M. Oostrom. ................................ 97
4.1 LNAPL observations ................................... 97
4.1.1 Discrepancyb etweenf ree productl evels in
monitoringw ells andL NAPL specificv olume ........ 97
4.1.2 Correlation of LNAPL well measurements to
LNAPL volume ................................ 107
4.2 Observationso f dissolvedN APL components. ............. 116
4.2.1 NAPL componentsp resenti n groundwatear t lower
than solubilityc oncentrationasn d fluctuationsin
concentrations ................................. 116
4.2.2 Upgradiento ccurrenceo f dissolvedN APL
componentvsi a gasp haset ransport ................ t 35
Relnediation
M. Oostrom,R , W. Falta, A. S. Mayer,
I. Javandel, and S. M. Hassanizadeh .......................... 141
5.1 Remediationm ethodologies. ........................... 141
5.2 Hydraulicr emovalo f LNAPL .......................... 146
5.2.1 LNAPL trappinga s free productm igratest owards
extraction well ................................. 146
5.2.2 LNAPL trappingi n the coneo f depression. ......... 151
5.2.3 Decreasei n free LNAPL recoveryr atesa s a function
of time ....................................... 157
5.2.4 Incompleter emovalo f residualL NAPL with
hydraulicm ethods. ............................. 163
5.3 Pump and treat ....................................... 169
5.4 Soil vapor extraction. ................................. 178
Notation ..................................................... 191
List of Figures ................................................ 197
List of Tables ................................................. 204
References ................................................... 206
Index ....................................................... 215
Preface
Awareness of the problem of soil and groundwater contamination by
nonaqueoups hasel iquids( NAPLs) begani n the late 1970st o early 1980s.T his
awarenessg rew out of observationtsh at sites,w hoser emediationw as predicted
to concludeo ver severaly ears,w ere nowheren ear meetingc leanupg oals,e ven
after decadeso f remediatione fforts.M any suchs itesw ere found to be contami-
nated with essentiallyim miscibleo rganicl iquids, sucha s petroleumh ydrocar-
bonsa nd chlorinateds olventsI.t was eventuallyr ecognizedt hat, due to their low
solubility,s mall amountso f thesel iquids had the potentialt o contaminatev ery
large volumeso f soilsa nd groundwaterF. urthermore,i t was recognizedt hat the
unevend istributiono f the liquidsi n the subsurfacec, oupledw ith the low solubil-
ity and relatively low flow rates of groundwaterw, ere giving rise to excessive
time framesf or remediationw ith typical cleanupg oals.
During the decadesth at followedt hesed iscoveries, intensiver esearche fforts
were dedicatedt oward investigatingt he flow, transport,a nd interphasem ass
exchangeo f NAPLs. These efforts have led to an enhancedu nderstandingo f
NAPL migrationi n the vadosea nd saturatedz ones,i mprovedc haracterizationo f
NAPLs as sourceso f groundwaterc ontaminationa, ppropriates ite investigation
techniquesfo r assessinNg APL contaminationa, ndb ettert echnologiesa nd strate-
gies for remediatingN APL-contaminateds ites.I n particular,p orousm edia het-
erogeneityh as been recognizeda s perhapst he single most importantf actor in
determiningN APL distributionst,h e subsequenftu nctiono f NAPLs as a source
of groundwatecr ontaminationa, nd the limiting factori n remediatingN APL-con-
taminated sites.
In this book, we presento verviewso f recenta dvancementws ithin the context
of a more completer eferenceo n the principleso f NAPL migrationa nd distribu-
tion for engineeringa nd scientificc onsultantsa, cademicsa, nd studentsW. e begin
by explainingt he fundamentalp hysicala nd chemicalp henomenat hat impact
NAPL transporitn the subsurfaceT.h e bookt hent akesa tutoriala pproachw, here
we posea probablef ield scenarioa, ndt hene xplaint he phenomenath at may have
createdt he scenariow ith appropriated iscussiono n the fundamentapl hysicala nd
chemicalp henomenao f concernT. he book introducesth e mostc ommonlyu sed
Soil and GroundwaterC ontaminationN: onaqueousP haseL iquids
Water ResourcesM onograph1 7
Copyright2 005 by the AmericanG eophysicaUl nion
10.1029/17WM00
vi MAYER AND HASSANIZADEH
equationsfo r describingN APL fate and transporti n the subsurfacef,o llowed by
numerical exampleso f the applicationo f these equations,a nd offers multiple
illustrations( with well over one hundredf igures)t o furthere xplaint he concepts
describedin the text. Numerouse xampleso f the applicationo f mathematicafl or-
mulasa nd analysesto assessN APL contaminationa re givena s well. The book is
supplementedb y a user-friendlyC D that containss preadsheetuss edi n many of
the examplec alculationsc, olor versionso f someo f the illustrationsa, nd movies
illustratingN APL migration.
This book is the result of collaborative effort between the editors and several
contributorsw ith a wide range of experiencei n teachinga nd in solving ground-
water contaminationp roblemsi n the laboratorya ndt he field. The editorso utlined
the book, solicited sectionsf rom the contributors, and edited the contributions to
producea n integratedb ook.
Co-editor Dr. Alex Mayer is a Professori n the Departmento f Geological &
Mining Engineering & Sciences, Michigan Technological University. Dr.
Mayer's Ph.D. in EnvironmentalE ngineeringi s from the University of North
Carolinaa t ChapelH ill, 1992. In additiont o his role as co-editor,D r. Mayer con-
tributedt o Chapter 1 and Sections3 .5, 4.2, 5.1, and 5.2. Co-editor Dr. S. Majid
Hassanizadehis Professoro f Hydrogeologyi n the Departmento f Earth Sciences
of Utrecht University,T he Netherlands.H e receivedh is Ph.D. from Princeton
Universityi n 1979. Also in additiont o co-editing,D r. Hassanizadehc ontributed
to Chapter 1 and Section5 .1.
The contributorsa nd their contributeds ectionsin cludet he following. Dr. Ron
Falta is a Professoro f Geology and EnvironmentalE ngineering at Clemson
University,S outhC arolina. Dr. Falta receivedh is Ph.D. in Mineral Engineering
from the University of California, Berkeley in 1990. Dr. Falta contributedt o
Sections2 .3 and 5.4. Dr. Tissa Illangasekarei s AMAX DistinguishedC hair of
EnvironmentaSl ciencea ndE ngineeringa nd Professoro f Civil Engineeringa t the
Colorado School of Mines. He received his Ph.D. in Civil Engineeringf rom
ColoradoS tateU niversityi n 1978. Dr. Illanagasekarec ontributedto Sections3 .2,
3.3, 3.4, and 3.5. Dr. Iraj Javandeli s a senior scientista t Lawrence Berkeley
National Laboratorya t the University of California. He receivedh is Ph.D. in
Civil Engineering/Hydrogeologfyro m the Universityo f Californiaa t Berkeleyi n
1968. Dr. Javandel contributed to Sections 3.5 and 5.3. Dr. Karsten H. Jensen,
M.Sc. and Ph.D. in Hydrology from the TechnicalU niversity of Denmark, is
currentlyp rofessora t the GeologicalI nstitutea t the Universityo f Copenhagen.
Dr. Jensen contributed to Sections 2.1, 2.2, 3.1, 3.2, and 3.3. Dr. Mart Oostrom
hasb eene mployeda t PacificN orthwestN ational Laboratoryf or almost1 0 years,
whereh e directst he Multifluid Flow ResearchL aboratoryD. r. Oostromr eceived
his Ph.D. from AuburnU niversity,A labama,i n 1991. Dr. Oostromc ontributedto
Sections 4.1 and 5.2.
Dr. Mayer wishest o acknowledget he supporto f the Fulbright U.S. Scholar
Program and a Visiting Professorshipa t the Delft University of Technology,
which were instrumental in the creation of this book. This book is based on
PREFACE vii
lecturesg iven at the advancedc ourseC ontamination of soil and groundwatebr y
nonaqueousp hase liquids (NAPLS)-Problems and solutions, 1-3 July 2002,
Delft, The NetherlandsT. he coursew as organizedb y Postgraduates choolP AO
of Delft University of TechnologyT. he editorsa re grateful to David Oostveen,
M.Sc. studenta t Faculty of Civil Engineeringa nd Geosciencesin Delft for his
assistancwe ith word processinga spectss ucha s referencinga ndi ndexing.W e are
alsog ratefult o the anonymourse viewer,w hoses uggestionws ere extremelyh elp-
ful. Finally, we wish to thank the staff at AGU books for their considerable
expertisei n publishinga nd for seeingt his projectt hrought o completion.
The editorso f this book wish to dedicatet his book to our belovedc ompanions:
Suzanne and Forooz.
Alex Mayer
Departmento f Geological & Mining Engineering& Sciences
Michigan TechnologicaUl niversity
S. Majid Hassanizadeh
Department of Earth Sciences
Utrecht University,T he Netherlands
Introduction
A significantp ortiono f contaminateds oil and groundwaters itesc ontainsn on-
aqueousp hasel iquids (NAPLs). NAPLs are hazardouso rganicl iquids that are
immisciblew ith water and form a visible, separateo ily phasei n the subsurface.
Their migrationi s governedb y gravity, viscousf orces, and capillary forces. If
NAPLs were truly insolublei n water,t heir impacto n groundwaterq uality would
be very limited. But, NAPL componentsc an dissolvei n water in very small
amounts( yet muchh ighert hand rinkingw ater limits) and at very low rates.A s a
result,g iven the high toxicity of NAPL componentsa, small volume of NAPL in
soil canf orm a long-termt hreatt o the groundwaterq uality.T hus, unlessp roperly
managed,N APLs can exist in the subsurfacefo r decadesa nd can contaminate
large volumeso f groundwaterH. owever,i t is very difficult to designe ffective
remediations chemesd, ue to the complexb ehavioro f NAPLs in the subsurface.
In fact, the presenceo f NAPL hasb een shownt o be a significantl imiting factor
in siter emediation[ EPA, 2003]. This is partly due to hydrogeologicfa ctors,s uch
as complexh eterogeneityp atterns,a nd the presenceo f low permeabilityz ones.
But more importantly,a nd tied with hydrogeologicf actors,i t is becauseo f the
very complexn atureo f the variousp rocessesth at affect the migrationo f NAPLs
and transporto f their dissolvedc omponents.
During the past few decades,a huge body of literature has developedo n
the occurrenceo f NAPL in the subsurfaceo, n the spreado f NAPL as a separate
phase and/or transporto f its componentsb y gas and water phases,a nd on
ways of containinga nd cleaningt he contaminationW. e do not intend to give a
reviewo f the literaturei n this monographB. ut, we will makee xtensiver eferences
to the publishedli teraturet hroughoutth e book. Here we give a very shortl ist of
variousc ategorieso f literaturet hat haveb eenc onsultedin this monographF. irst,
there is a myriad of papers that have appearedi n joumals and conference
proceedingsA. lso, nationall aboratoriesa, genciesa, ndi nstitutesh avec ontributed
extensivelyt o the body of literature in this area. In particular, publications
by the AmericanP etroleumI nstitute,A PI, have treatedv ariousa spectso f NAPL
pollution and remediation (see, e.g., API [1986]; Charbeneaue t al. [1999]
Huntley and Beckett[ 2002b], [2004]; Sale [2001]; or the API LNAPL web site,
http://groundwatear.p i.org/lnapl/). Also, the U.S. Environmental Protection
Agency (EPA) has published a large number of reports on NAPL in the
subsurface(s ee, e.g., EPA [2003]; Parker et al. [1995]; Sabatini et al. [1996];
Soil and GroundwaterC ontaminationN: onaqueousP haseL iquids
Water ResourcesM onograph 17
Copyright2 005 by the AmericanG eophysicaUl nion
10.1029/17WM01
2 MAYER AND HASSANIZADEH
Wilsone t al. [1990];o r theE PAC LU-IN webs iteh ttp://clu-in.orgE/)P. Ah asa lso
publisheodu treacdho cumenwtsh, iche xplainp ollutioann dr emediatioisns ueisn
a simpllea nguag(see ee, .g.", TheC itizen'Gs uides" eriesh,t tp://clu-in.org/products/
citguide/A). numbeorf specializetedx tbookinsc ludes ectionosn N APLf lowa nd
transpoirnt soila ndg roundwat(esre ee, .g.,B edienet t al. [1999]C, orey[ 1994],
Fetter[ 1999],H elmig[ 1997],P ankowa ndC herry[ 1996]).T herea rea fewb ooks
thatd eals pecificalwlyi thN APLr emediatiomne thodsE.x ampleasr eN yere t al.
[1996]a ndS impkine t al. [1999]A. publicatioonf particulainr teresfto rr emedia-
tion issuesis the monograp"hA lternativefso r GroundwateCrl eanup"b y the
National Research Council [1994].
Thep urposoef thisb ookis t op rovidteh eb ackgrounfodr s olvinpgr acticaplr ob-
lemsc oncerninNgA PL contaminatioannd r emediatioTnh. eb ookd iscussepsri n-
cipleso f multiphafsleo w,t ransfeorf NAPLc omponentots w atera ndg asp hases,
andt heirt ransporint the subsurfacWe.h erea principleis introducedit,s sig-
nificancteo practicapl roblemss,u cha s sitei nvestigatioannsd r emediationis,
discusseSdp. eciaal ttentioins paidt o the roleo f heterogeneitiine sth e spatial
distributioonf NAPLs.C onceptasr ei llustratedw ith the aid of graphsd, rawings,
andp hotograpThhs.e b ookd escribewse ll-establishceodn ceptbsu, ta lsot heg aps
in ouru nderstandionfg N APLsa t thef ield scalei,l lustratewd ith examplefsr om
field,l aboratoroy,r modelinsgt udiesM. anys ituationtsh ata tf irsts eemto b ec oun-
terintuitivaer ed escribeda,n dt hena ree xplainedw ith the aid of basicp rinciples.
Exampleosf counterintuitsiviteu ationinsc ludeth ep resencoef LNAPL( lighter-
than-wateNrA PL)b elowg roundwattearb leo r upgradienotc currencoef d issolved
NAPL components.
Thisb ookw ill be usefutl o a wider angeo f audiencesIt. canp rovidep racticing
engineerasn ds cientiswtsh oa rei nvolveidn NAPLc ontaminatiaonnd r emedia-
tions tudiews itht hen ecessarbya ckgrounIdt .c ans ervea sa referencoen multi-
phasefl ow andt ranspoprth enomenfoar professiona(els.g .c onsultanatns d
regulatorwsh) oa rec oncernwedit he valuatinogrr emediatinNgA PL-contaminated
sitesI.t canb eu seda sa supplemetnot g roundwatoerr hydrogeologcyo urswe ork
foru pper-levuenl dergraduoart bee ginninggr aduatset udentIst .i s assumethda t
ther eadehr asa backgrounedq uivalentot anu ndergraduactoeu rsien quantitative
groundwatehr ydrology.
Thisb ookc onsistosf fourm ainc haptersIn. Chapte2r , basicp rincipleosf multi-
phasfel owa ndc ontaminatnrat nspoirnt poroums ediaa rep resenteind a concise
mannePr.r opertieasn dp arameterress ponsibfloer them igratioann d/otrr apping
of NAPL ared escribedV.a riousin terphasme asstr ansfepr rocesseasre i ntroduced
andm ulticomponetrnatn spomrt echanismarse e xplainedIn. Chapte3r, thei nter-
playo f hydrogeologfaicc torws ithN APLc haracteristiisc dse scribeind o rderto
explainc omplexp atternosf NAPL distributioinn the subsurfacPeh. enomena
sucha sp oolingt,r appinugn detrh ew atert able,p ermeabilibtya rriersu,n stable
frontsa, ndf ingeringa red escribeadn de xplainedIn. Chapte4r , commoonb ser-
vationsa ssociatewdi th monitoringa nd assessmeonft sitesc ontaminatewdi th
NAPLsa red escribedin, cludinogb servationosf N APLsi n monitorinwge llsa nd
INTRODUCTION 3
soil samplesa nd observationso f NAPLs dissolvedi n groundwater.F inally,
Chapter5 dealsw ith ther emediationo f NAPL-polluteds itesA. ttentioni s focused
on issuesa nd phenomenaa ssociatedw ith three standarda nd widely-applied
methodologiesT. hese are: hydraulicr emovalo f NAPL (separatep haser emoval
of LNAPL via wells or trenches),p ump-and-treat( extractiono f groundwater
containingd issolvedN APL componentsv ia wells) and soil vapor extraction
(extractiono f gasp hasec ontainingv olatilizedN APL components).