Subsurface Solute Transport Models and Case Histories TheoryandApplicationsofTransportinPorousMedia SeriesEditor: JacobBear,DepartmentofCivilandEnvironmentalEngineering, Technion – Israel Institute of Technology, Haifa, and School of Engineering, KinneretCollegeontheSeaofGalilee,Israel Volume25 Forfurthervolumes: http://www.springer.com/series/6612 Vyacheslav G. Rumynin Subsurface Solute Transport Models and Case Histories With Applications to Radionuclide Migration ABC VyacheslavG.Rumynin TheRussianAcademyofSciences InstituteofEnvironmentalGeology SaintPetersburgDivision SaintPetersburgStateUniversity GeologicalDepartment SredniyAve.,41,of519 199004St.Petersburg RussianFederation [email protected] This book is a revised and updated version of the book in Russian Geomigracionnye modeli v gidrogeologii (Geomigration Models with Application to Groundwater Hydrology), by Vyacheslav G. Rumynin, published by “Nauka” (“Science”) Publisher, St.Petersburg,2009,ISBN978-5-02-025140-3. ISBN978-94-007-1305-5 e-ISBN978-94-007-1306-2 DOI10.1007/978-94-007-1306-2 SpringerDordrechtHeidelbergLondonNewYork LibraryofCongressControlNumber:2011930258 (cid:2)c SpringerScience+BusinessMediaB.V.2011 Nopartofthisworkmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorby anymeans,electronic,mechanical,photocopying,microfilming,recordingorotherwise,withoutwritten permissionfromthePublisher,withtheexceptionofanymaterialsuppliedspecificallyforthepurpose ofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework. Coverdesign:deblik Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface Studiesofsolutefateandtransportinthesubsurfaceenvironmenthavebeenplaying asignificantroleinhydrogeologyoverthepasthalfcentury.Theproblemdirectly relates to the quality of natural water resources, which are essential to all kinds oflife, andare a basic elementin manysectorsof humansociety.Mostmigration studies of both naturaland anthropogenicallyderivedspecies have consideredthe motionofafluid(groundwater)accompaniedbydiffusion–dispersionphenomena, physicochemicalinteractions,aswellasmicrobiologicaltransformations,knownto be the dominant factors providing the impact of contaminants upon groundwater supplies. Overthelastdecades,essentialprogressinthemigrationprocessdescriptionhas beenachievedduetothedevelopmentofmathematicalbackgroundandnumerical methodsandlaboratoryandfieldinvestigationsofparticulartransportmechanisms andphysicochemicalinteractions.However,inmanyrealsituations,thesubsurface materialheterogeneityandvariationsinfluidproperties,resultinginnonlinearcon- taminant plume behavior, make the prediction accuracy of the transfer processes toolowtosatisfythepracticalneeds.Thelackofcomprehensivefieldstudiesofso- lutemovementisoftencitedasamajorimpedimenttoourunderstandingofsolute transportinsuchsystems. Therefore,thisworkisaimedatthedevelopmentofthebasicknowledgeofthe subsurface solute transfer with a particular emphasis on field data collection and analysis coupled with modeling (analytical and numerical) tool application. The book is based mostly on field materials from author’s long-standing, recent, and current experience in the study of groundwater quality related problems. The di- versity of these problems is concerned with the variety of geological settings as well as the anthropogenic effects and processes caused by human activity. Some problemsencounteredinpracticelookedaschallenge-likeand,thus,theauthorwas encouraged to search for new solutions and approaches. The relevant theoretical developmentsareconcernedmainlywiththeformulationandsolutionofdetermin- isticmass-transportequationsforawiderangeofengineeringissuesingroundwater qualityassessmentandforecastingthatcanbeofsomeinterestforbridgingthegaps stillexistinginourknowledgeofcontaminanthydrogeology. The book gives many computation examples and case studies drawn from the conductedfieldinvestigations.Thoseexamplesshowtheapplicabilityofthetheory v vi Preface and methodsfor solving variouspractical problemsand making decisions in con- taminanthydrologytoexplaintheobservedandtoforecastthefuturegroundwater quality.Theanalyzedproblemsareasfollows: (1) investigation and prediction of groundwater contamination by industrial con- taminantsandsolutions(radionuclides,chlorideandnitratebrine)withspecial focus on the effect of (a) aquifer heterogeneity,anisotropy,and dual porosity, (b) density contrast between industrial waste and groundwater, (c) physico- chemical interactions that play a major role in retarding (e.g., adsorption) or enhancing (e.g., interactions between dissolved species and mobile colloids) contaminanttransport; (2) prediction of the effects of pumping on groundwater quality at wellfields: (a) the displacement of stratified initial concentration in artesian and coastal (off-shore)groundwater systems due to water pumping, (b) downward move- ment of mineral-weatheringproducts in the vadoze zone (above the lowering watertable)withwaterrechargetotheproducingaquifers; (3) groundwater dating using stable and radioactive isotopes for prediction and assessment of contamination potential and the time that would be needed to displacecontaminantsfromthegroundwatersystem; (4) fieldandlaboratorytests’ designandanalysis,andmonitoringdatainterpreta- tion; (5) partitioningofsurfaceandsubsurfaceflowsusingisotopetechnique; (6) formationofevaporatedsaltdepositsinclosedsurfacewaterreservoirshaving ahydraulicconnectionwiththesurroundinggroundwatersystems. Severalpartsofthebookdemonstratethepotentialforusingnumericalground- water flow and transport models in environmental risk assessment of subsurface contaminationbydenseorlightmiscibleliquidwaste.Environmentalisotopedata were utilized for defining the groundwater systems and modeling data analysis. However, numerical modeling emerged in the book mostly as one of the primary toolsusedtounderstandthemostimportantphysicalandphysicochemicalprocesses thatoccuringroundwatersystems,aswellasforgettinganalyticalapproximations forsomecoupledproblems,whichdonotnecessarilyhaveexactsolutionsinclosed analyticalformsorcannotbetreatedwiththeclassicalmethods. Oneofthemostessentialtopicsaddressedinthebookisthemigrationandfateof radionuclides.Modeldevelopmentismotivatedbyfielddataanalysisfromanumber ofradioactivelycontaminatedsitesintheRussianFederation:near-surfaceradioac- tivewaste (RW)disposalsitesinnorthwesternRussia andtheSouthernUrals,and two deep-well RW injection sites in Western Siberia. These sites are partof huge nuclear industry enterprises licensed to possess radioactive materials and also in- volvedinhazardous-wasteoperations,whicharesupervisedbyRosAtom,theState NuclearEnergyCorporation,RussianFederation. Thetotalactivityofradionuclidesthatwerereleased(accidentallyorintention- ally) in aquifers at many sites reaches hundredthousands to hundredmillions Ci. AnyofthethreeRWdisposalsitesoutofthefourmentionedhere(locatedinSouth- ern Urals and Western Siberia) probablycontains more radioactive contamination Preface vii inthesubsurfacethananyothersiteintheworld.Additionally,detailedinformation onphysical,mechanical,andsolutetransferpropertiesofclayformation(whichis consideredasahostmediumfortheengineeredundergroundRWrepositoryinthe northwesternpartoftheRussianFederation)isalsoanalyzed. Thosesitesplayauniqueroleintheadvancementofknowledgeofthesubsurface behaviorandfateofmanyhazardousradionuclidesandcanbeconsideredasfield- scalelaboratories.Thebookisfocusedonthemodelingandanalyticalassessments ofarangeofphysicalandchemicalprocessesandinteractionsofconcern.Someof thekeyissuesneededtobeaddressedincluded: (1) studyofthebehaviorofabroadspectrumofradionuclides(fissionproductsand actinides) in waste (with low content of dissolved solids and brine) based on long-term(upto50years)monitoringdatainshallowanddeepaquifersystems; (2) studyofthespatialvariabilityofmigrationpropertiesofaquifermaterialsand clayeysemiperviousformations; (3) assessmentoftheroleofbrine-inducedadvectioninredistributionofradioactive componentsatwastedisposalsites; (4) studyofadsorptionhysteresisimplyingisothermnonsingularityandothernon- ideal sorption phenomena, as well as the assessment of their role in natural attenuationofradioactivelycontaminatedsites; (5) analysisoftransienthydrogeochemical-barriereffects,facilitatingradionuclide transport,andsomeothermechanismsresponsiblefor“fast”radionuclidetrans- portinaquifers; (6) experimentalevidence for colloid-facilitated radionuclide(actinide) transport, andmathematicaldescriptionofthephenomena. The model developmentswere accompanied by laboratory studies into natural attenuation, radionuclide adsorption and desorption kinetics and equilibrium (in- cluding when colloidal particles are involved). Batch tests were conducted with differentradioactivesolutionsunderdifferenttemperatureandpressureconditions. Anomalousbehaviorofradionuclideswasobservedandmodeled. Thisstudycanberegardedasthecontinuationofaseriesofworksstartedbythe authorinthe1970sincooperationwiththeoutstandingRussianscientist,hydroge- ologist,V.A.Mironenko,whosecontributiontothedevelopmentofseverallinesof studiesinhydrogeologyandhydrogeomechanicsisdifficulttooverestimate.Atthe sametime,thisbookcouldnotappearedwereitnotfortheall-roundsupportfrom colleagues–researchersfromE.M.SergeevInstituteofEnvironmentalGeology,St. PetersburgDivision,RAS,andSt.PetersburgStateUniversity,whorenderedassis- tance in the preparation of parts of the book. In this connection, the author very much appreciatesthe help of Leonid Sindalovsky in implementationof many nu- mericalalgorithmsconsideredinthebook,thecontributionofPavelKonosavskyto the joint studies of adsorption hysteresis and the developmentof some models of solutetransferintheporousmediaunderdisturbedflowconditions.Theauthoralso appreciatesIgorTokarev’swillingnesstosharehisdataonregionalisotopestudyof agroundwatersystemintheareaofRWdisposalatTomsk-7site. viii Preface The study discusses experiments carried out in laboratories of A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, RAS, and A.P. Alexandrov TechnicalInstituteundersupervisionofDrs.ElenaZakharova,ElenaKaimin,and ElenaPankina.Theauthorexpresseshissinceregratitudetothesegroupsforcoop- erationthathaveyieldednewresults. The author appreciatesthe cooperationof Aretech Solutionsand TIHGSA En- terprisesallowinghimtolearnnewhydrogeologicalaspectsrelatedtotheformation ofgroundwaterresourcesandqualityinaridregions. The author also much appreciates the attention to his work and fruitfull dis- cussions with Profs.Vsevolod Shestakov and Sergey Pozdniakov, Moscow State University, and Dr. Andrei Zubkov, the head of the EnvironmentalProtection Di- vision(SiberianChemicalPlant),andmanyotherbrilliantexperts–hydrogeologists, whosetalentandenthusiasminscientificandproductionworkallowstheauthorto believeinthefutureoftheRussianhydrogeologicalschool. ManyeffortsweremadebyDr.Chin-FuTsangandProf.JacobBeartoorganize thisworkinaproperwayinordertopreparethebookinaformatacceptableforthe internationalpublishingcompany,Springer.Discussionsandexchangeofinforma- tion,ideas,andopinionswiththemwasagreatsupporttothiswork. Finally,theauthorverymuchappreciatesthehelpofDr.GennadyKrichevetsin professionaltranslationofthebookandmanyusefulcommentsfromhimallowing theauthortomakecertainimprovementstothebook.Theauthorwouldalsoliketo acknowledgethehelpofEkaterinaKaplanforhereditorialassistanceandtechnical supportofthework. Thus,thebook,alongwiththeoreticalfindings,containsfieldinformation,which willfacilitatetheunderstandingofsubsurfacesolutetransportandthedevelopment of a methodology for practical application to groundwater hydrology. This book addressesscientistsandengineerswhoareinterestedinthequantitativeapproachto studyinggroundwatermigrationprocesses.Thebookcanalsobeprofitablyreadby students. December28,2010 VyacheslavG.Rumynin Contents PartI TheEssentialsofDissolvedSpeciesTransport intheSubsurfaceEnvironment:BasicDefinitions,Fundamental MechanismsandMathematicalFormulation 1 AdvectionandDispersionofDissolvedSpeciesinAquifers ............. 3 1.1 GoverningEquationsandSoluteTransportParameters.............. 3 1.1.1 Advectionof ConservativeComponents inPorousandFracturedMedia .............................. 4 1.1.2 MolecularDiffusionand Hydrodynamic Dispersion(Microdispersion)................................ 11 1.1.3 InitialandBoundaryConditions;Definitions ofConcentrationFunctions .................................. 18 1.2 ModelsforAdvectiveTransportinHomogeneous IsotropicMedia......................................................... 20 1.2.1 ACharacteristics-BasedMethodforSolving theTransportEquations...................................... 20 1.2.2 Solute Transport Process Analysis inCurvilinearCoordinates................................... 24 1.3 AOne-DimensionalModelofMicrodispersion...................... 33 1.3.1 SolutionsforInfinitePorousDomain........................ 34 1.3.2 A Basic (Fundamental) Solution forSemi-InfinitePorousDomain............................ 36 1.3.3 On the Solutionand Analysis of Solute TransportProblemsbyApplyingtheLaplaceTransform .. 38 1.3.4 Quasi-One-Dimensional Solution ofMicrodispersionProblemsinDeformed FlowsinPorousMedia....................................... 45 1.4 Spatial (2D and 3D) Modelsof Microdispersion inUnidirectionalSteady-StateFlow .................................. 46 1.4.1 BasicSolutionsforaPointSource........................... 47 1.4.2 ApproximateSolutionsfor2Dand3DSolute TransportProblems........................................... 50 1.4.3 Steady-StateAsymptotics.................................... 52 ix x Contents 1.4.4 ApproximateSolutionsforaFinite-SizeSource............ 54 1.4.5 ExactSolutionsfor3DProblem............................. 57 1.4.6 TheInfluenceofGeologicalBoundaries.................... 58 1.5 EquationsforSimplestChemicalReactionsandTransformations .. 60 1.5.1 Sorption....................................................... 60 1.5.2 Decay.......................................................... 64 References...................................................................... 70 2 WaterMovementandSoluteTransportinUnsaturated PorousMedia.................................................................. 77 2.1 BasicSoil-WaterMovementandInfiltrationModels................. 78 2.1.1 GoverningFunctionsandParameters........................ 79 2.1.2 ContinuityEquationanditsMajorRepresentations ........ 85 2.1.3 ParticularSolutionsforMoistureMigration andTheirAnalysis............................................ 88 2.2 OnModelsCouplingWaterInfiltrationandSoluteTransport .......106 2.2.1 Advection:ACharacteristicSolution........................107 2.2.2 DispersionDuringAdsorptionofWaterbySoil............111 2.2.3 Advection–DispersionTransport ............................114 References......................................................................116 PartII ConceptualModelsforRegionalAssessment ofSoluteTransport (UnderHomogeneousLiquidFlowConditions) 3 One-DimensionalHydrodynamicMixing Models for RegionalFlowSystemsUnderArealRechargeConditions andTheirApplicationtotheInterpretationofIsotopicData ...........123 3.1 StableComponentMigration..........................................124 3.1.1 FlowandMassBalanceUnderConfinedFlow Conditions ....................................................124 3.1.2 BasicAnalyticalSolutions...................................125 3.1.3 Correspondencewitha ReservoirModel: TransitTimeandTransitTimeDistribution.................128 3.2 TransportofaSoluteSubjecttoFirst-OrderSingle-StageDecay ...131 3.2.1 BasicAnalyticalSolutions...................................131 3.2.2 VariableBoundaryConditions...............................132 3.3 MigrationofaSoluteSubjecttoChainDecay........................135 3.3.1 Two-Stage Chain Decay of an Unstable Isotope Coming into an Aquifer with InfiltrationRecharge..........................................136 3.3.2 Two-StageChain Decayin Aquiferwith aRadioactiveElementinSolidsastheOnly SourceofRadioactivity ......................................139 3.3.3 Two-MemberChainDecayinAquiferSolids ContainingSeveralRadioactiveElements...................141