JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 104, NO.

B10, PAGES 22,985-23,003, OCTOBER 10, 1999

Formation of natural gas hydrates in marine sediments

1. Conceptualmodel of gas hydrate growth conditioned
by host sediment properties
M. BenClennell,
•'2MartinHovland,
3James
S.Booth,
4
Pierre
Henry,
sandWilliamJ.Winters
4

Abstract. The stabilityof submarinegashydratesis largelydictatedby pressureandtemperature,

gascomposition, andporewatersalinity.However,the physicalpropertiesandsurfacechemistry
of deepmarinesediments mayalsoaffectthethermodynamic state,growthkinetics,spatial
distributions,andgrowthformsof clathrates.Our conceptual modelpresumes that gashydrate
behavesin a way analogous to ice in a freezingsoil.Hydrategrowthis inhibitedwithin fine-
grainedsediments by a combination of reducedporewateractivityin the vicinityof hydrophilic
mineralsurfaces,andthe excessinternalenergyof smallcrystalsconfinedin pores.The excess
energycanbe thoughtof asa "capillarypressure" in thehydratecrystal,relatedto the poresize
distributionandthe stateof stressin the sedimentframework.The baseof gashydratestabilityin
a sequence of fine sediments is predictedby ourmodelto occurat a lowertemperature (nearerto
the seabed)thanwould be calculatedfrom bulk thermodynamicequilibrium.Capillary effectsor a
buildupof saltin the systemcanexpandthephaseboundarybetweenhydrateandfreegasintoa
divariantfield extendingovera finitedepthrangedictatedby totalmethanecontentandpore-size
distribution.Hysteresis betweenthetemperatures of crystallization
anddissociation of the
clathrateis alsopredicted.Growthformscommonlyobservedin hydratesamplesrecoveredfrom
marinesediments(nodules,andlensesin muds;cementsin sands)can largelybe explainedby
capillaryeffects,butkineticsof nucleation andgrowtharealsoimportant.The formationof
concentrated gashydratesin a partiallyclosedsystemwith respectto materialtransport,or where
gascanflushthroughthesystem,mayleadto waterdepletionin thehostsediment.
This"freeze-
drying"maybe detectable
throughphysicalchanges
to thesediment (low watercontentand
overconsolidation)
and/orchemicalanomaliesin the porewatersandmetastablepresenceof free
gaswithinthenormalzoneof hydratestability.

1. Introduction Gas hydratesrecoveredfrom beneaththe seafloordisplay a

wide range of growth habitsand tend to be patchily distributed
Current models for the formation and distribution of gas within the host sedimentaccordingto texture [Ginsburg et al.,
hydratesin marinesedimentsgenerallyassumethat the phase 1993: Ginsburgand Soloviev, 1994, 1997; Boothet al., 1996].
equilibriaof a bulk water and gasmixture(Figure 1) measured While the baseof hydratestability in the marine subsurfacehas
underlaboratoryconditions [Dholabhaiet al., 1991;Dickensand often been found at the approximateconditionsof pressureand
Quinby-Hunt, 1997] can be applied directly to the natural temperature given by bulk phase equilibria [Hyndman et al.,
environment[Kvenvolden,1993; Dillon et al., 1993; ?aull et al., 1992; Trdhu et al., 1995], there are a numberof ocean drilling
1994].(By bulkwe meana bodyof materialof sufficientsizethat sites where the depth range over which hydrates occur is
local fluctuationsin propertiesaverageout, and surfaceenergy narrowerthan that predicted[ Westbrooket al., 1994; Paull et al.,
terms are small compared with other contributionsto free 1997]. The sedimentsomehowinhibits gas hydrate nucleation
energy.)However, laboratorytestsdo not cover the rangeof and growth,an inferencesupportedby experimentaldataon gas
pressures foundin natureand bulk pressure-vessel experiments hydrateformationin porousmedia [e.g.,Makogon,1981; Yousif
do not accountfor effectsof host-sedimentpropertieson hydrate and Sloan, 1991; Handa and Stupin, 1992; Melnikov and
stability.Accordingto Hyndmanet al. [1992, p. 292] "...therole Nesterov,1996]. Here we review the evidencefor host-sediment
of clay surfaceactivity and the fine pore spacesin deep sea effects on the stability and growth habits of gas hydratesand
sediments is unknown."
proposesomeexplanations.
Ginsburg [1998] distinguishestwo categoriesof submarine
gas hydrates:thosewhich occurthroughoutthe sedimentoften
• Department
ofEarth
Sciences,
University
ofLeeds,
England.
2NowatCentro
dePesquisa
emGeoffsica Universidade extendingdownto the baseof hydratestability(deepseated),and
eGeologia,
Federal da Bahia, Salvador. Brazil. local, concentratedaccumulationsassociatedwith focused gas
• Statoil,
N-4035,Stavanger,
Norway. flow featuressuchas mud volcanoes(seepagerelated).While we
4UnitedStates
Geological
Survey,
Woods
Hole,Massachusetts. can make some inferencesaboutthermodynamicstability from
5Laboratoire
deG•ologie,
EcoleNormale
Sup•rieure,
Paris.
hydratesthat lie close to the phaseboundary,the shallower
Copyright1999by theAmericanGeophysical
Union.
manifestationstell us that gas can move up throughsediments
withoutnecessarily combiningwith waterto form clathrates.
It is
Papernumber1999JB900175. importantto view naturalgashydratesin thisperspective.There
0148-0227/99/1999 JB900175509.00 is a particular set of conditions controlling equilibrium
22,985
 22,986 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1

6O place under strong thermal gradients within the soil (several

methane & seawater
5O
, methane & pure water
• 4O
Hydrate + water
a• 30
• 20 /
lO
Gas + water
o
5 lO 15 2o
Temperature (øC)
Figure 1. Simplifiedphasediagramshowingthe stabilityfield
of pressureand temperaturefor gas hydratesunderconditions
foundin the marinesubsurface assumingpuremethanegasand
seawater fluid composition. Solid arrows indicate the
displacementof the phase boundary line to higher pressure
and/or lower temperatureif gas hydrate is inhibitedby some
mechanism.
thermodynamicstabilityin a certainsedimentat any depth,but a
generalmodelmustalsoallow for possibledisequilibriumarising
from limitationsof reactantsupplyandtransport,andthe kinetics
in nucleationand growth of gas bubblesand hydrate crystals.
Here we examinethe quasistaticequilibriumbetweenphases,and
we make qualitative predictions about the system behavior
through time. Our approach is complimentary to porous-
continuum models [Rempeland Buffett, 1997, 1998; Xu and
Ruppel, 1999], which quantify the dynamic equilibrium that
evolveswhen fluxes of methane,water and heat passthroughthe
sediment column.
Sincethe structureof naturalgashydratesis similarto that of
water ice [Sloan, 1990], we develop the analogy between the
formationof naturalhydratesand the processes that occurduring
freezingin porousmedia and in.permafrostin soils.A numberof
authors[e.g., Trofirnuket al., 1972; Pearson,1981;Ershovet al.,
1993] have alreadynotedthat segregated formsof gashydratein
fine sedimentsclosely resembleice lensesthat grow in fine-
grainedsoils,while in coarsersediment,hydratesgrow within the
poresand cementthe grainsstronglytogetherso that loosesand
becomes"frozen solid" with commensurate changesin physical
properties [Pearson et al., 1983]. MacDonald et al. [1994]
degreesCelsiusper meter),with the thermodynamic drive for the
transportof water to the point of crystal growth coming from
undercoolingof the waterbelowthe normalfreezingpointwithin
the sediment pores [Konrad and Duquennoi, 1993]. The
temperaturegradientsin deepoceansedimentsare typically0.02-
0.08 øC m-] so thatanother
thermodynamic
drive,namely,
supersaturationdue to an excessof methaneor undercooling
belowthe normalequilibriumtemperature,is neededto produce
concentratedaccumulationsof gas hydrates.Nevertheless,the
thermodynamics underlying freezing in porous solids, as
! describedby the capillary-icemodelof Everett[ 1961], providea
good startingpoint for the analysisof gas hydrateformationin
sediments.
Followingsomeobservational andtheoreticalbackground, we
describe a model of gas hydrate stability based largely on
principlesfrom soil physics.In a companionpaper,Henry et al.
[this issue] developour conceptualmodel to make quantitative
25 3o predictionsof gas hydratestability,and theseare testedagainst
observations of gashydrateoccurrenceat the Blake Ridge from
OceanDrilling ProgramLeg 164 [Paull et al., 1997].
2. Bottom Simulating Reflectors and the Gas
Hydrate Phase Boundary
The inferredbaseof gashydratestabilitybeneaththe seafloor
is often markedby a seismicreflectorwith negativeimpedance
contrast[Stoll et al., 1971;Shipley et al., 1979]. Given that gas
and fluid compositionchangelittle with depth,and that the fluid
pressureprofile is very close to hydrostatic[Hyndmanet al.,
1992], the reflectorcan be takento representa univariantphase
boundarythat is nearly isothermaland roughly parallels the
seafloor. Accordingly, it is known as the bottom-simulating
reflector(BSR).
There is somedisputeas to the physicochemical regime that
producesthe BSR [Brown et al., 1996]. Hyndrnanand Davis
[1992] and Hyndman and Spence [1992] suggestedthat the
reflectionaroseat the boundarybetweena hydrate-bearinglayer
with high-velocityoverlyingsedimentswith a normalvelocity.In
several localities it has been shown that the BSR more likely
marksa boundarybetweenoverlyingsediments containinga little
hydrate and an underlyinglow-velocity zone, typically a few
metersto many tens of metersthick, in which there is a small
proportionof free gas in the pore space[Miller et al., 1991;
MacKay et al., 1994; Singhet al., 1993;Andreassen et al., 1995;
Hovland et al., 1997]. The latter situationis shownin Figure 2.
Below the depth of intersectionbetweenthe geothermand the
phaseboundary,methanein excessof aqueoussolubilitywill be
presentas a free gas phase(bubblesin the sediment).Between
this depthand the seafloor,hydratewill fill someproportionof
the sedimentpores providing there is enoughgas availableto
stabilize the clathrate structure.

document gas hydrate outcropson the seafloor of the Gulf of The primary indicatorof gashydratestabilityconditionsis the
Mexico that are similar in size and appearance to permafrostice positionof the BSR, as existingmodelswould predictthat gas
lenses. first appearsat the depth limit of hydratestability,that is, the
There are important differences between hydrates and thermodynamicthree-phaseequilibrium. The P,T conditionsof
permafrostice. We needto take into accountthe presenceof a gas the phaseboundarycan be deducedfrom measurements of the
phase(dominantlymethane),which,unlikeair in soil,participates thermalgradientandthe total depthto the BSR beneathsealevel.
in the formation of the crystalline solid. The availability of This locusof pressureandtemperature canbe comparedwith the
methanemay limit the hydrate-formingreaction,but we will also gas hydrate stability curve calculated or measured in the
describe circumstances where water laboratory for the particular gas and fluid compositions
limitation drives the
dynamicsof the system.Ice lensformationandfrostheavetake prevailing.If the BSR shouldbe at a higher,coolerpositionin the
 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1 22,987

, •*•,• Seabed

Stability iiiiiiiiil!iiiiiiiiiii•iiiiiiiii•i•iiig"i•i•i•i•i•:
'•i•i•i•ili•i•i•i•iii•i•i•i•i•i•ii•i•i

/--un•••
0iiiiiiiiiii•ililli
iii! ,:;:,:,,,,,
,:,,:,,:,:,,
,:,,=,:,:,:,:.:,:.:,:.:.:.:.:.:•,:,:,:,:,,
.:.:.:.:':':':][':':':':':.:.:::F."-'•:F•.
:::::::::::::::::::::
:::
Geotherm Free gas

Figure2. Conventional
modelfor gashydratestabilityandbottom-simulating
reflectors
in submarine
sediments.
Thebaseof hydrate
stability
is markedbya univariantphaseboundaryastemperatureincreases
deeper intothe
sediment.
At thispointmethane in excess
of solubility
in watermayexistasfreegasandpotentially
produce a
distinctseismicreflectordueto reducedvelocity.

sedimentcolumnthanthe predictedphaseboundary,thenwe can rangeof hydrate.A greaterpressureor a lower temperature is

deducethat either somemechanismis inhibitinggas hydrate
stabilityor the systemis out of thermal,hydrostatic,
or chemical
equilibrium. On the otherhand,to explaina BSR thatliesdeeper
than expected (warmer conditions) either requires some
mechanismthat promotes hydrate stability or a dynamic
mechanism preventingattainment of thermodynamicequilibrium.
One mechanismof inhibitionthat hasbeenquantifiedis the
depression of wateractivitydueto the presenceof salts[Dickens
and (•uinby-Hunt,1997]. Seawater(whichis composed of many
saltsbut depresseswater activity to approximatelythe same
degreeasa 1 M NaC1solution),typicallyreduces theequilibrium
temperature of thepuremethane+ purewaterphaseboundaryby
1-2øC.Methanehydratestabilityis promoted verystronglyby the
presenceof even small amounts of ethane, carbon dioxide,
hydrogensulfide, and higherhydrocarbons.
For example,1%
ethane would approximately counterbalancethe effect of the
seawaterinhibition.Theseshiftsof a few degreesCelsius,would
at normal thermal gradientscorrespondto a changein the
positionof the BSR of tens of meters.Severaldisequilibrium areain theseexperiments.
effects could producechangesof this order: active tectonics, We arguethatnoneof the previousexperimental studiescan
migratingwarmeror coolerfluids,incompletediffusionof salt beapplied
that is excludedfrom the hydratestructureout into the pore the porousmatrix used was rigid and/or had an unrealistic
waters,or changesin bottomwater temperatureand sea level influence
duringglacial cycles.The predictionsof our equilibriummodel presenceof a freshratherthansalineporewater,whichleadsto
mustbe viewedin the contextof thisnaturalvariability. markedexpansion
3. Previous Studiesof Gas Hydrate Formation in
Porous Media
Experimentsshowthat porousmediamodifythe stabilityof
clathrate hydrates according to the pore size and surface
propertiesof the host material [Makogon, 1981; Sloan, 1990;
Yousifand Sloan, 1991;Handa and Stupin,1992;Zakrewskiand
Handa, 1993; Bondarevet al., 1996, Makogon, 1996;Melnikov
and Nesterov,1996].The porousmediumdecreases the stability
necessary to form the hydrate, and a lower dissociation
temperatureis observedon warming,than is the caseunderbulk
conditions.
Valuesof up to 8øCarereportedfor thedepression in
meltingtemperature
of gashydratesin microporous
silicaglass
[Handa and Stupin, 1992]. Similar values were found for
experiments in clay by Melnikovand Nesterov[ 1996].Bondarev
et al. [1996] foundthat the meltingpoint of tetrahydrofuran
hydratein loamwasdecreased by upto 2øC.
Handa and Stupin [ 1992] concludedthat the hydratein a
porousnetworkbehaves in muchthe sameway asice,a premise
we developlater.BothHanda and Stupin[1992] and Melnikov
and Nesterov[ 1996]showthatthe enthalpyof formationof gas
hydrateis decreasedin porousmedia, and this is in the same
proportionas measuredbetweenbulk ice and pore ice. The
inductiontime for hydrateformationin porousmediais reduced
with respectto formationin free solution,andagitationis not
requiredto inducenucleationof hydrate[Makogon, 1981;Yousif
andSloan,1991].Thisis attributedto thelargegas-watersurface
directlyto themarinesubsurface.
Oneproblem is that
fromsurfaceproperties dueto its composition,
or the
of the bound-water layer.The particular
physicalconditionsemployed,andthe phasedistributions
that
prevailed
in theseexperiments
arealsodifferent
fromthoselikely
to apply in situ. Yousifand Sloan [ 1991] assumedthat the
presenceof a freegasphasewithintheporousnetworkis needed
to formtheclathrate,
andtheyignorethethermodynamic effects
of confinementin poreson the hydratephaseitself.Handaand
Stupin [1992] considereda water or ice-saturatedmedium in
equilibriumwithanexternal gaspressure.
Witha 7 nmporesize,
capillarypressure
on the liquid-water
interfaces
is sohighasto
preventintrusionof free gasinto the porousnetwork.Equal
 22,988 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1

pressuresmay thus be assumedfor the externalgas and for the [Kastner et al., 1996]. The soupy layers have on average a
water insidethe pores,but there is no direct controlof the water coarsertexturethan the non-hydratedsediments,but the trend is
pressure. not definitive (A. Camerlenghi,personalcommunication,1994.)
Submersibleexperimentsovercome some of the problems The "soupy"layerswere interleavedwith sedimentsthat were
encounteredin replicatingin situ conditionsin the laboratory.In overconsolidated, frequentlyfracturedandanomalouslydry, with
experimentsreportedby Brewer et al. [1997], methanegaswas one silty clay sampledriedto the pointof losingall cohesion so
bubbledthroughtubescontainingcoarseand fine sediments.In thatitstextureresembledgroundcoffee.
the coarsesediment,gas flow spreadout and hydrateprecipitated 4.2.2. Leg 164: Blake Outer Ridge. ODP Leg 164 was
widely within the pore space,cementingthe sedimentinto a solid dedicatedto the studyof gas hydrates[Paull et al., 1997], and
mass. In the mud sample, gas flow was restrictedto a few includeda transectof three sitesin the Blake OuterRidge I¾oma
channelsformedas gasstringerspushedup throughthe sediment. regionwith no discernible BSR (Site994) to areaswith moderate
Gas hydrate precipitationwas initially limited to the sidesof (Site 995) and strong (Site 997) BSRs. Gas hydrates were
these"pipes"and a few localizedpockets,and then thesepore sampledin many places,chiefly occurringin the form of small
spacesand fracturesformed by the passageof gas beganto fill crystalsdispersedin the sediment.Indirect evidenceof gas
with hydrate. These experimentsmodel conditionsprevailing hydrateswas alsoobtainedfrom loggingand geochemical data
close to the seabedwhere the sedimentdoesnot experiencea from all three sites. Chloride depletionprofiles suggestthat
significantconfiningpressure. around1.5-6% of the pore spaceis filled with hydratebetween
about 200 and 450 meters below the seafloor [Dickens et al.,
1997], while concentrations exceeding10% of the pore space
4. Observationsof Natural Gas Hydrates and occur in several depth intervals.Independentestimatesfrom
Their Host Sediments loggingshowgoodagreement [Paullet al., 1997].
The lithologyin this regionis monotonous, consistingmainly
4.1. Shallow Cores and Dredge Sampling of siltyclaysandcalcareous oozes(Figure3d). The poresizesof
two typical sediment sampleswere measuredby mercury
Gashydrateshavebeenrecoveredfrom shallowcoresin many
injection[LowellandShields,1991].Poresdiameters rangefrom
sitesaroundthe world's oceansand deeperlakes [Kvenvoldenet
a few nannometresto a few microns,the mode being 80 - 150
al., 1993]. Gas hydratehas been observedas a cementin sands
nm;Figure4. Largerporesareprovidedby cavitiesin microfossil
and sandstones (e.g., Kuparuk Sandsof Alaska, [Collett 1993]).
shells.Zones of increasedhydratedeterminedby the chloride
Findingsfrom numerouslocalitiesaroundthe world summarized
proxyappearto correlatewith sedimentary horizonsthat havea
by Booth et al. [1996, 1998] show that gas hydrates more
highercontentof siliceousmicrofossils[Kraemeret al., 1997],
typicallyoccurin the form of segregated bodies:lenses,nodules, while G.D. Ginsburg el al. (Ginsburg, G.D., Soloviev, V.A.,
pellets,or sheetswhere the host sedimentis fine-grained(clays
Matveeva, T. and Andreeva, I., Sedimentgrain-sizecontrolon
andsilts),andapparentlyonly displayan interstitialor cementing gashydratepresence,ODP Sites994, 995 and 997, submittedto
habitin coarser-grained lithologies[Boothet al., 1996; Brookset Proceedingsof the Ocean Drilling Program, ScientificResults,
al., 1994; Ginsburget al., 1993; Ginsburgand Soloviev,1994, 1999), analyzinggrain sizesof the pore-watersqueezesamples,
1998]. identify a weak but positive correlationbetween the reported
degreeof fresheningandthe proportionof coarsersilt fractions.
4.2. Deep Ocean Drilling
The thermal profiles derived from downhole temperature
4.2.1. Leg 146: Cascadia Margin. Sites 889/890 offshore measurements indicatethat the positionof the BSR is colderand
Vancouverand 892 offshoreOregonpenetratedthe zone of gas shallowerthanthat predictedfrom bulk equilibria,with 1ø to 3øC
hydrate stability into an underlyingzone bearing free gas undercooling,corresponding to 30-100 m of depthoffset, in the
[Westbrooket al., 1994; Carsonet al., 1996• MacKay et al., case of the methane hydrate-seawatersystem [Ruppel, 1997].
1994]. At both sitesthe top of the free gaslayerwas foundto lie There is someevidencethat the first appearanceof hydrate,at
abovethe depthpredictedfrom bulk stabilitycalculations
using around190 m, is deeperthan predictedfrom in situ gas content
thethermalprofilesfromtheholes(40-50 m higherthanthepure measurements (G. Dickens,personalcommunication, 1998).
water-methanephaseboundaryand 10-20 m higher (perhaps 4.2.3. Leg 170: Costa Rica. At Site 1041, which lies at 3300
0.3ø-0.6øC cooler) than the likely seawater-methanecurve m water depth offshore Costa Rica, gas hydrates were
[Kastner et al., 1995; Whiticar et al., 1995]. Sedimentsat both encountered in almost every core recovered between
localities were predominantlyfine grained (clayey silts) with approximately120-280m belowseafloor,accompanied by strong
occasionalsand layers. The sedimentsare uncleformedin the porewaterfreshening[Kimuraet al., 1998].Massivehydratewas
slopebasinsandapron(shownin Figure3a), but the underlying foundin intervalsof fracturedclaystonesand siltstones,andthin
accretedmaterial is highly tectonizedand has widely variable sheets of hydrate could be observed within the fractures
textureandphysicalproperties. themselves (Figure3b). The corefacesandfracturesurfacesalso
Small pelletsof gas hydratedisseminated
in silty clay and fizzed for several minutes after recovery. Some of the
occasional massive pieces were observed in the shallow effervescencecame from spotsof hydratevisible with the hand
subsurface
of Site 892. Geochemical, physicalpropertiesand lens,but in mostcasesthe sourcewas apparentlydiffusewithin
downhole-loggingdataindicatethat gashydratesare probably the sediment pores. The hydrate-bearinginterval contained
disseminated
in small quantitiesthroughout
the stabilityzone several volcanic ash layers. In each ash layer there were
[Westbrooket al., 1994; Hovland et al., 1996; Whiticar et al., indicationsof the presenceof hydratein the pore space.In two
1996]. There are alsoindicationsthat hydrateswereconcentrated intervalsthe ash was stronglycementedby gas hydrate(with
at a numberof horizonsat both sites. Severallayershad a possiblysome water ice) so that it was impossibleto break
"soupy"or mousse-like
appearance,
andthesewereinterpretedto withouthard blows from a hammer.Oncethe hydratehad melted,
be horizonswherehydratehaddissociated duringcorerecovery the ash crumbledto fine dust that was rather dry to the touch.
 CLENNELL ET AL.' GAS HYDRATES IN MARINE SEDIMENTS, 1 22,989

(a) (b)

1 cm
1 cm I I I

(c) (d)

(e)
Figure 3. Hostsediments of gashydratesfromoceandrilling.(a) Shallowclayeysedimentfrom ODP Hole 892E,
0.5 metersbelowseafloor(mbsf), Cascadiamargin,showingopen"honeycomb" pore structure.Conventional
scanning electronmicrograph. (b) Clayeysilt fromsamehole,2 mbsf.Low vacuumscanning electronmicroscope
(SEM) imageof undriedsediment.Note largeporespresentbetweenaggregates, smallporeswithin particle
aggregates, and shelterporesassociated with microfossils. (c) Massivehydrategrowingeither as displacive
"lenses"or fillingfractures
morepassively withinfirm clayeysilt,ODP Hole 1041A,120mbsf,CostaRicamargin.
(d) Bandedvitric ashcompletelycemented by pore-fillingclathratefrom Hole 104lB, 235 mbsf.(e) Very fine
grainedsiltyclayfromODP Hole 995A, 350 mbsf,BlakeRidge.Sediment typeis typicalof the deeperhydrate-
bearingsectionin thislocality.SEM imageof freeze-dried sample.

theashymaterialtogether(Figure 5. Thermodynamics
Thatis, thehydratecemented in PorousMedia
3c).
Insideporousmediathe thermodynamic potentialof chemical
On thispartof the CostaRicamargin,the geothermal gradient componentscan changewith respectto bulk conditionsas a
is so low that the hydratephaseboundarywould lie below the consequenceof (1) Molecular interactionsat the pore walls,
maximumdepth of drilling. Thereforewe have no information usuallyattractionof the fluid moleculesby hydrophilicmineral
from the positionof a BSR as to whetherthe sedimentproperties surfacesand (2) The energy required to maintain capillary
wereinfluencing thethermodynamic stabilityof thehydrates. equilibrium.
 22,990 CLENNELLET AL.' GASHYDRATESIN MARINE SEDIMENTS,1

Mercury entry point to major pore mode: 5.2. Capillary Effects

ß•, lO5 correspondsto gas water capillary
entry pressureof approx. 1 MPa Capillaryeffectsoccurwhenimmiscible,mobilephasesco-
• 104 existwithina porousmedium.A mobilephasedoesnothaveto
be a fluid: it can be a deformable solid that flows in order to
• 103 minimize free energy.Capillary equilibriumis a mechanical
'-
I:L 102 balancewherea differencein pressurein phaseseithersideof an
interfaceis supported
by a surfacetensionforcein the interface
--•
.m 1 01 region.The interface
regionhasa freeenergyexcess
or surface
o• 1øo I I I I
energy
associated
withit. Surface
tension
(N m-1)andspecific
o 20 40 60 80 10o
surface
energy
(J m'2)aredimensionally
equivalent,
having
the
samenumberin SI units.The amountof surfaceenergyin a mass
% Hg Saturation of materialis definedby curvatureof the boundingsurfaces. The
(a)
total curvaturetc of a surface(Figure6) can be describedat any
pointby theradiirl andr2 of twoprincipalarcsof curvature
that
intersect
orthogonally
at thatpoint[Davis,1996]:
• 18 Largeporemodecorresponds
--=16 [] togasexpansion
cracks
and •c=(1/rl+l / r2) {1)
• / ,,,, surface
roughness
"o Poresize distribution For eachpairof phases(A andB) in contactwithina pore,the
12
'• ! ; 1[i •• peaks radiusdifferencein phasepressures
atpore is the productof thecurvature,
tCA•,
andspecificsurface
energyof theinterface
7•.
-•
"-'

E
8
6

4
' The pressure
difference
whichexistsacross
Ps - PA = YABK AB

the curvedphase
(2a)

"- 2
interfaceis termedthe capillarypressure,and(2) is the Young-
-• 0
100 10 I 0.1 0.01 0.001

(b) (0.1
mm)Pore
Diameter
(micrometers)
(1nm)
Figure4. Mercuryinjectionporosimetry
datafor claysamples ...................
i: ,5' •ii'.
........... X

from the Blake Ridge, ODP Hole 995A, 350 and 546 mbsf. - ............... ::i :- , X
Pore-sizedistribution(volumeintrudedthroughprogressively •'.............
,,, ,, .... -::•,,::::.:-,:-,:
.... x Mineral grainswith
smallerporethroats)determined
usinga cylindrical
poremodel .....
-:..---'..•:,ii'
' "' -"':ii:
.................
'•" x negative surface
and the differential of the cumulative volume intrusion curve; ':•:
..........................
"x\ '.-'• '•::
....................
' x• charge
.... 'i •
mercury
surface
tension
0.484N m-l, entrycontact
angle140ø.
Samples
werefreezedriedto preventshrinkage.
............
" \ (• ':i::•. X

-xnm•, ß
.............. • - / .... '-• :•:'• Bound water

5.1. Surface Potentialsand Depressionof Water Activity :',i•."•':'"::..,.

'.........
"t / / • ', • ...... Osmotic,
loosely
...............
:• / • -, bound
Partial ordering and bonding of water molecules with
hydrophilicmineral surfacesdepresses water activity (activity • (•) • Free
water
with
beinga measureof chemicalpotentialnormalizedto a reference
state).Nitao and Bear [1996] give a rigorousdescriptionof the
energypotentialsof liquid water in poroussediments. Marked
•(•)•)•/• Cation
neutral
solution
in pore bodies

depression of water activity in poresa few nanometers acrossis

attributedto large proportionof moleculesbeing adsorbedon
Profile of Pore Water Activity
surfaces[Zharikov, 1994].
Depressionof water activity is also significantin sediments 1.0-
containingclays,due to their largespecificsurfaceareaand the
pronounced
ionic doublelayer that thesemineralsdevelop
Osmotic
depression
of aw in free solution

[Mitchell, 1993] (Figure 5). The consequenceis that reactions

involvingwaterare inhibitedwithin clay suspensions andin fine-
grainedsediments.For example,aqueoussolutionsmay become
supersaturated within a clay bed, while mineralsare precipitated
preferentiallyin adjacentcoarser-grained layersin whichthe pore Bound:::: Partly ordered Free solution
fluids have normal water activity [Tardy and Novikoff 1988; water water molecules
Putnis et al., 1995]. We predict that hydrate formation in fine-
grainedand more clay rich sedimentswill be inhibitedby water
Distance from surface
adsorptionparticularlywhen gas saturationis high. The surface
potential effect will add to the osmotic depressionin water Figure 5. Distribution of capillary, bound and free water in
activity of dissolvedsalts[Dickensand Quinby-Hunt,1997] and sedimentlayers and nature of the diffuse bound water layer
canbe treatedin a similarway thermodynamically. aroundclay particles.Basedon Mitchell [1993].
 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1 22,991

Where bt.
ø is the chemicalpotentialof thatcomponent
l under
rl bulk conditions(zero curvature).A curvedinclusionof material,
suchasa dropof liquid,thushasa higherchemicalpotentialthan
a largemassof the samesubstance.The totalchangein chemical
potentialof a phaseis thengivenby an extendedGibbs-Duhem
equation:

dG= -SdT+ VdP

+7dA
+•i btidni (5)
Making certainassumptions aboutthe ideality of the fluid
phases(perfectgasesor dilute solutions)we can make some
thermodynamic substitutions
and arriveat a generalrelationship
referred to as the Kelvin or Gibbs-Thomson equation that
Convex: rl, r2 > 0 Saddle: rl < O, r2 > 0 expresses
the chemicalpotentialrelativeto the bulkmaterialasa
function of mean surface curvature:

Figure6. Definition
of totalcurvature
andtheprincipal
planes
of curvatureof a surface.The two principalradii of curvature
definable
at anypointmaylie onthesamesideor onopposite ln-•-fi-=
FmRTICy (6)
sides of the surface.
Equation(2) meansthat small inclusionsor convolutedmasses
with a positive mean curvature,or nonwettingfluids with a
convex meniscusin a tube or porousmedium have a higher
pressure thana surrounding fluid phase.Equation(6) impliesthat
Laplaceequation.
On thesurface
of a spherer• = r2 = r, sothe theyalsohavegreaterchemicalactivity,higherequilibriumvapor
total curvatureis 2/r. On the surfacea cylinderof radiusr, oneof pressure,and greater solubility in solventsthan the same
the radii of curvatureis infinite, so the total curvatureat the walls substance in bulk. A specialform, referredto as the Ostwald-
inside a long, cylindrical pore is l/r. However, the end Freundlichequation,is usedto expressthe relativesolubilityof
termination of an inclusion within a cylindrical pore is a crystalsof differentsizes,asexplainedin section6.4.
hemispherical
cap,andthe curvature
of thisinterfaceis 2/r, the
sameasfor an inclusionfilling a sphericalpore. 5.3. FreezingPoint Depressionof Liquidsin PorousMedia
The signconvention is suchthatr• and r2 in (1) arepositive The freezingpointof wateris depressed in fine-grained
porous
whentheiroriginslie in the B phase,so convexinclusions like mediasuchas soilsrelativeto bulk conditions.This undercooling
bubbleshave positivesurfacecurvatureand positivecapillary is an equilibriumthermodynamic effect,observablealso during
pressures internally.The relativeattraction
or repulsion of the melting, and is unrelated to possible supercoolingdue to
fluid phasesto the internal surfaceof the medium,or its difficultiesin nucleationkinetics(see below) that may alsooccur
wettabilitymustalsobe specified.Wettabilityis expressed as a
in bulk water. Undercoolingin porousmediais attributedto the
contactanglesubtended between thesurfaceandtheliquidphase:
higherattractiveforcesgiveriseto wettingcontactanglesof less presenceof curvedice-waterinterfacesthat increasethe free
than 90ø and or surfacefilms, while non-wettingphases(less energyof poreice relativeto bulk ice [Everett,1961].Porewater
attractedthan a co-existingwetting phase,or repelled by the behavesas a wettingphase;mostmineralgrainsare coatedwith a
moleculesof the solid surface)have a contactangle greaterthan thin film of water 5-50 nm thick that remains unfrozen, while ice
90ø [Davis,1996].In a tubeor porousmedium,the differencein is stronglynonwettingand formsconvexshapeswithin the pores
pressurebetweena wettingA phaseand nonwettingB phase that minimize surfacearea [Churaev et al., 1993]. The wetting
(superscriptsWandNW,respectively), with the contactangle0anglebetweenwater and mineralgrainsis effectivelyzero:that of
measured throughthewettingphaseis the nonwettingice is 180ø [Miller, 1980]. Ice hasa higherphase
pressurethan water whenthey are in thermodynamic equilibrium
NW W
P/•,
pore- Pff--7/lB
r/t/•cos
0surface (2b) within a pore.
In the small pores found in a silt or clay sediment, the
The capillarypressure acrossa curvedinterface curvatureof the interstitialice is necessarilygreat,andthe surface
discontinuity
representsa mechanicalenergybalance,but the Gibbs free energyexcessis considerable.Conversely,in coarsesediments
energiesare also affectedby surfacecurvature,by an amount like sandthe thermodynamiceffect is almostnegligiblebecause
the radiusof curvatureis large.Figure7 showsthe situationwhen
givenby the changein surfaceenergy.In differentialform,the
ice fills a large sphericalpore and with further freezing grows
rate of increasein surfaceenergyis ¾dA,while the changein
into an adjacentcylindrical pore of smaller radius. From the
surfaceareaA is equalto tcdV.Thetotalchangein volumeis the Young-Laplaceequation(2b) the pressureof ice in contactwith
sumof the changesin partialmolarvolumeof eachchemical water can be calculated:
componentin thephasemultipliedby thenumberof molesof that
component: 27iw
Pi = Pw+ cøsOiw (7)
re
dl/--•i Vidn
i (3)
Pt and P,• are the ice and water phase pressures,y•,v is the
The changein chemicalpotentialof any onecomponent in a interfacialenergyper unit area,and re is the effectiveporeentry
mobilephasecanbe relatedto totalsurfacecurvature
andto the radiusaccountingfor the unfrozenwater film thickness.For this
statementof capillary pressureto be applicable,the ice must
partialmolarvolumeoccupied
bythatcomponent.
adopta curvedinterfaceon entry to the poreandtheremustbe a
= (4) uniform internal phasepressurein the ice [Miller, 1980]. The
22,992 CLENNELLET AL.' GASHYDRATESIN MARINESEDIMENTS,1

, %

30-

Nonfreezing
bounwater
Freezing
u rve

Melting
curve
•% •

m
I I I I i I
0 -1 -2 -3 -4 -5 øC

Temperature

Figure 7. Capillarymodelof porefreezing.Ice existswithin a largeporebody (idealizedas a sphericalcavity),

and with furtherdepression in temperatureadoptssufficientsurfacecurvatureto penetratean adjacentporethroat
(idealizedas a cylinder);that is, riw = r e. Inset, basedon •i//iams and Smith [1991], showsthe proportionof
unfrozenwaterduringfreezingandmelting;this curveexhibitsconsiderable hysteresisbecauseice massesin pore
bodies(effectiveradiusrb) are largerthan the effectivethroat sizes(re) that mustbe penetratedfor progressive
freezing to occur. In our analysisthe contactangle for ice Oiw is assumedto be 180ø (water wet pores: ice
nonwetting).

former assumptionis verified by microscopicobservations. producean undercooling

of severaldegrees
Celsius(insetgraph
Churaev et al. [1993] and Adamsonand Gast [1997] refer to in Figure7).
experimentswherea hemispherical cap ratherthancrystalfaces When the temperatureincreases,it is the effectiveradiusof
terminatesice insidesmall capillarytubes.The convex,rounded, curvatureof the largerporebody,rb in Figure7, that determines
ice-water and ice-air interfacespredictedby Miller [1980] are the melting point of the pore ice. Therefore,dependingon the
shown in photomicrographsof frozen bead packs [Colbeck, shapesof the pores, considerablehysteresiscan occur between
1982]. The secondassumptionis justified by the low yield meltingandfreezingcurvesin porousmedia[Jallutet al., 1992],
strengthof ice closeto its meltingtemperature and is knownas and both freezing and melting will occur over a range of
the "plastic ice" criterion [Everett, 1961' Gunnink and EI- temperatures up to the bulk meltingpoint(Figure7).
dayyousi,1993].The mechanisms by whichpressure is equalized
are referredto as solid statecreep.Scherer [1993] suggeststhat
5.4. Combining Capillary and Surface AdsorptionEffects
the main creep process in ice is diffusive mass transfer
accompanied by a someintracrystalline
deformation. The relationship between capillary effects and surface
Combingthe Kelvin equationwith the Clapeyronequationfor adsorptioneffectsis exemplifiedby membranepressexperiments
the thermodynamic ice-waterequilibrium[Everett,1961'dallutet wherean initially saturatedsoil (or sediment)sampleis subjected
al., 1992], the depressionof freezing point of water in a pore to a gaspressure[Bruandand Prost, 1987; Tessletet al., 1992].
relativeto the bulk freezingpoint can be calculatedas a function Water may escapefrom the far sideof the membraneand thus is
of the poreentryradius,re' kept at atmosphericpressure.Soils with a rigid framework of
27iwTi,bulkCOS 0iw sandor silt and thoseclayswith a low specificsurfaceareaand
ATi,pore= (8) layer charge, such as kaolinite, will be invaded by the gas,
piAHf ,ire resultingin capillary equilibrium. On the other hand, fine soils
HereTi,bulk is theabsolutemeltingtemperature of bulkice(273.15 rich in expandableclayssuchas smectiteswill compactunderthe
K), p, thespecificdensityof waterandAH/:,thespecific enthalpy gaspressure,and the smallpore size will preventintrusionof gas
of fusionof ice. The angleOiwsubtended at the porewall is 180ø up to high pressure(more than 10 MPa). The former type of
if ice is assumedcompletelynonwetting.A typical clay-bearing media are known as solid-solid framework soils, and the latter
silt hasporesin the 0.1 ½msizerangesore in eqn.(4) is typically type aretermedcolloidalsoils[Miller, 1980].
about10-7m [Griffithsand Joshi,1989].Substitution of the These two different responsescan both be describedas the
relevant thermodynamic properties(y,,,= 26.7mJm'2;Tt,bulk -- consequenceof changes in water activity, which can be
273.15 K;P,v= 1000kgm_3; AH/:,= 333kJKg-•) gives avalue of substitutedfor the chemicalpotentialon the left-handsideof (6).
AT = -0.425øC [Gunnink and El-Jayyousi, 1993]. Clayey In the solid-solidframeworksoil the Young-Laplaceand Kelvin
sedimentswith boundwater layers about 0.5 - 1 nm thick have equationsgive the equivalencebetweenthe maximumsizeof the
effective pores sufficiently small (tens of nannometres) to water-filled pores, gas capillary pressure,and water activity. In
 CLENNELL ET AL.' GAS HYDRATES IN MARINE SEDIMENTS, 1 22,993

the colloidalsoil, the depression pore sizes rather than as an additional effect that should be
in wateractivityis the samebut
is causedby the osmoticeffect of the increasinglysalineandaccountedfor separatelyin the equations[see Henry et al., this
moretightlyboundwaterremainingin the particleinterlayersasissue]. We wish to deal with casesin which hydrateis presentin
freshetwater is squeezedout. For example,a maximumwater- the porous network, and coexistswith water, so the capillary
filled pore radiusof 100 •m corresponds description is probably more appropriate. Equally, we must
to a gas capillary
pressure always be aware of the fundamentallydifferentphysicochemical
of 1.6 MPa andto a wateractivityof 0.988 [Tessieret
al., 1992]. Water adsorption and mechanicalstatesthat sedimentsof differentmineralogyand
effectsthusappearas an equivalent
materialswith very small texturemay exhibit.
to capillaryeffectsfor compressible

6. Capillary Model of Gas Hydrate Growth in

(a) NaCI Porous Media

A simplifiedphasediagramfor the H20-CH4-NaCI systemis

shownin Figure 8. Accordingto this diagram,(and a classical
interpretationof the Gibbsphaserule), gascannotexist as a free
phasewithin the zone of gas hydrate stability while water is
presentin excessexcept when the pore water is highly saline
[Zatsepinaand Buffett,1998]. Were gasto exsolvelocally dueto
NaC ß ingressor in situproduction,it would rapidly combinewith water
to form more hydrate [Sloan, 1990; Paul! et al., 1994]. We
examine the two-phase equilibrium between hydrate and
methane-saturatedwater before consideringthe effects that
--G confinement in sedimenthason the [gas+ water]/ hydratephase
boundary.
H20 CH4
H+L (H) H+G+L H+G 6.1. Two-Phase [Hydrate+Gas Saturated Waterl Equilibrium
Theory and experimentssuggestthat hydratecan nucleateand
(b) grow from aqueous solutions that are near to saturation or
metastablysupersaturated with respectto methane,without free
gas being present[Handa, 1990; Mashirov et al. 1991;Melnikov
'. • -H+G+L and Nesterov, 1993; Tohidi et al., 1995; Zatsepinaand Buffett,
L ',• ....
.-".'".-'•-'•-'•
.•••- 1998]. The likely kinetic mechanismfor the formation of gas
hydrate also requires that the methane molecules dissolve in
water before they can be incorporatedwithin the clathratelattice
[Lekvamand Ruoff, 1993]. Moving away from the three-phase
c• ,,/ H+L n+a boundaryinto the two-phasehydrate-stableregionby increasing
pressureand/or decreasingtemperaturereducesthe aqueous
H20 CH4'53/4
H20 CH4 solubility of methane, resulting in a greater proportion of
clathrate for a given amount of total methanepresentand an
• CompositionX increasein occupancyof gas moleculesin the clathratecages
[Handa, 1990].
Figure 8. (a) Ternary diagram of the methane-waterNaC1
systemappropriatefor the P-T rangeshownin Figure 1. This is Calculations of the two-phase equilibrium under P,T
a schematic diagram showing only the topology of phase conditionsappropriatefor submarinehydratesshowthat methane
coexistence and the main univariant and divariant fields. The solubility decreasesupwardsfrom the base of hydrate stability
solubility of methane in water is actually limited to mole towardsthe seafloor[Tohidi et al., 1997;Zatsepinaand Buffett,
fractions of about 0.001 to 0.0025, so the scale in the water rich 1998]. If methane-bearing watersadvectupwards,progressively
corner of the diagram is strongly distorted. The hydrate more gas can be extracted from the water to form hydrate
compositionshown is approximatefor full occupancyof the [Rempeland Buf•tt, 1997, 1998; Ginsburgand Soloviev, 1997].
type I clathratestructure.(b) SchematicT-X sectionthroughthe Even in the absenceof fluid advection,the progressiveupwards
ternary diagram for P approximately 20 MPa, and T
decreasein solubility will also produce a chemical potential
approximately 10-25 øC. Solid lines show the binary system
CH4-H:O [see Melnikov and Nesterov, 1993]. The dotted lines gradienttending to draw methaneupwardsthroughthe hydrate
show the possible influence of capillarity on the phase stabilityzone by diffusionin the porewater [Rempe!and Buffett,
equilibrium in the binary system. Water-rich initial 1997, 1998].
compositionsrequire undercoolingbefore pore hydrate can
form, whereas in gas rich compositions, capillary 6.2. Pressuresand Temperatures Within the Hydrate
supersaturationmay promote hydrate stability. Dashed lines Stability Zone
applyto a fluid compositioncontainingan appreciablequantity
of dissolvedNaC1, which decreasesthe temperatureof hydrate Assumingthat water forms a continuouswettingphasein the
formationand leadsto "saltingout" of a free gas phase[cf., poresand that the systemremainsopenwith respectto transport
Zatsepinaand Buffett,1998]. At lower temperaturesthan shown of methane,salts,andwater,thenthe aqueousphasepressurewill
here, salt+hydratecoexistenceis possible,and at temperatures be maintained(or buffered) at a value very closeto hydrostatic
below 0 øC, water ice and hydrohalite (NaC1.2H20) can be pressure.This assumptionis reasonableeven in the presenceof a
stablephases[de Roo et al., 1983]. modestwater flux in a sequenceof compactingsediments[Xu
 22,994 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1

andRuppel,1999].Theporewaterpressure
isthengivenby solubilityin that part of the sedimentcolumn.Condition2 could
be achievedif the pore fluids are overpressured; though this
Pw-- Pwg(
z + h) (9) violatesthe assumption of hydrostaticpressuresandopensystem
wherePwis the densityof theporewater,g is theacceleration
due conditions.Condition3, supersaturation of methanein the pore
to gravity,z is the depthin the sedimentcolumnandh is the water,couldoccurif formationof gasbubblesis alsoinhibitedby
water depth. In hydrate-stableregionsbeneaththe oceanthe capillaryeffects.The behaviorof a freegasphaseis considered in
hydrostaticpressure of the waterwill generallyrangefrom 5 to section6.7. Within the two-phaseregion, the requirementfor
50 MPa. supersaturation meansthat less hydrate will form for a given
With waterpressure
stipulated
asthereference
pressure
in the amountof gas,andthe thresholdamountrequiredto form hydrate
open-system stabilityzone,hydratephasepressure becomesthe at any depth[Handa, 1990]will be reduced.The first appearance
dependent variablein (2b). The phasepressure of non-wetting of hydrate going down into the sedimentis controlledby the
hydrateentirelyconfinedwithinthe porespaceis givenby the balanceof methaneproductionand upwardsflux to a sink in the
sum of the hydrostaticreferencepressureand a "capillary" zone of methaneoxidation closeto the seabed[Borowskiet al.,
component,dictatedby the mean surfacecurvatureof the 1996]. The depth where methanefirst reachesthe threshold
crystals.
The curvature changesin a complexway according to amountto precipitatehydratewill be deeperin a sedimentpile
poresizedistribution, percentagefilling of the porespace,and affected by inhibition than would be predicted by a bulk
growthhabit,butremains positive.
In a finelyporous mediumthe thermodynamic model[Tohidiet al., 1997].
capillarypressure
of hydratemaybe a significant
proportion
of
For example,if the surfaceenergyfor hydrate 6.4. Nucleation of Hydrate Inside PorousMedia
the totalpressure.
is similarto thatof waterice,about30 mJm'2,wefindthatin a To form hydrates, dissolvedgas moleculesmust combine
cylindrical
poreof 50 nmradius,thecapillary
pressure
of hydrate togetherwith watermoleculesin a clusterof sufficientsizefor
will be of the order of 1 MPa. the free energychangeof the reactionto overcomethe surface
We haveassumed,loosely,a linearthermalgradientthrough energyof the new interface.The clusterof critical size has an
the sedimentpile. This implies that heat flow and thermal energyexcessthatjust balancesthe excesschemicalpotentialof
conductivityareconstantwith depth,themis negligible advectionthe reactingcomponents. This clusteris the nucleusfor further
of heatby movingporefluid andthatthereaction to formhydrate growth, which is energeticallyfavorable becausethe excess
itselfdoesnotperturbthethermalstructure(i.e.,themis a kindof chemicalpotentialof the crystaldecreases as its radiusincreases.
static equilibrium).The water chemicalpotentialis then a In hydrates,the thermodynamicdrive to overcomethe energy
predictablefunctionof depthwhile open-system equilibrium barrierassociatedwith nucleationcomesfrom supersaturation of
prevails.The sediment poresizeandmineralogy mayvaryfrom the water with methane. Supersaturationmay result from
place to place within the sediment,leadingto different increasedsupply of methane, increasedpressure,or reduced
contributionsto the energy state of the water from surface temperature.We can expressthis relationshipbetweencluster
interactions.However, theseperturbationscan be balancedby sizeandsupersaturation usingthe appropriateform of the Kelvin
minor variationsin salinityand microscalefluctuations
in fluid equation:
densitythatequalizetheoverallchemical potential[Miller,1980;
Nitao and Bear, 1996].This is why we consider
the waterphase
to be "buffered"in a referencestatein an opensystem.
insS•
=27V,n r RT (11)
Sr is the saturationof the pore fluid in equilibriumwith
6.3. CapillaryInhibitionof GasHydrateGrowth nucleating
crystal
of radius
r, whileSOisthebulksolubility,
or
in Porous Media
saturationat equilibriumwith a flat surface.
Accordingto the precedinganalysisfor ice, hydratefmxned The two possiblemechanismsfor appearance of a new phase
insideporesis lessstablethanbulk hydrate.The formationof are homogeneous nucleation,wherea clusterformsin the bodyof
clathrates
in thetwo-phaseregionis inhibitedby capillaryeffects, the liquid, andheterogeneous nucleation,wherethe clusterforms
and an extra thermodynamicdrive is requiredto promotethe on a third surfacesuchas a gas bubbleor a mineral substrate
reactionwherebywatercontainingdissolved methaneconverts to [Adamsonand Gast, 1997]. The level of supersaturation required
solidgashydrate: for homogenousnucleationis normally much greaterthan that
requiredfor heterogeneous nucleation.
CH4(aq) +nH20(liquid)--methane hydrate(solid
) (10) Drawing analogywith the freezingof water [Scherer,1993]
Here n is a stoichiometriccoefficient,equalto about5.75 for full andthe crystallizationof salts[Putniset al., 1995] insideporous
occupancy of Type 1 methanehydrate,Sloan[1990].We suggest media, we believe that it is extraordinarily unlikely for
threepossible waysto overcome theinhibition: homogeneousnucleationof hydrate to occur in isolatedsmall
1. Undercooling with respect to the bulk equilibrium pores.We considerthat homogeneous nucleationand efficient
temperatureat a given pressure,becausereaction(10) is growth under diffusion-limited conditions can only occur in
exothermic. larger pores or fractures, and then the maximum degree of
2. An extra pressureon the liquid phasereactantsrelativeto inhibitionis not set by the pore size of sedimentsbut by the size
bulk equilibriumat a given temperature becausereaction(10) of the criticalhydratenuclei.
involvesa netvolumeloss(AV<0) underlikelyP,T conditions. For ice, the radiusof the criticalnucleusis about2 nm, but this
3. Supersaturation of the aqueoussolutionwith respectto will not appearuntil a supercoolingof up to 40øC is attained
methane. [Churaevet al., 1993]. In gas hydratereactors,the size of first-
Condition 1 can be achievedif the baseof hydratestability formednucleiis estimatedfrom laserlight scattering to be 5-30
migratesupwardsin the sedimentcolumn.Thiswouldproducea nm [Higskole et al., 1994]. Chefsky and Mikhailov [1989]
shallowerthan normal BSR where gas is presentin excessof calculate the equilibrium size of the first-formed nucleusfor
 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1 22,995

clathrates.
For a supercoolingof up to 10øCtheypredicta critical anisotropyof the in situ stresses.The cohesionof uncemented
radiusfor hydratein equilibriumwith methane-saturated waterof sedimentis generally negligible with respectto the confining
about 7 nm, and for a supercoolingof IøC a radius of stress,but lithified sedimentsmay have a tensile strengthof
approximately 70 nm. Thus in the absenceof a significant severalmegapascals. The segregationcriterionin (12) will only
thermodynamic drive from supersaturation theremay be a space be met wherethere is a wide rangein pore sizesincludingpores
problemwhennucleating methanehydrateswithinthe poresof with very narrow throats;that is, in clays and silts, where pore
compacted claysandsiltsthatareonlytensof nanometres across sizes will be in the nanometersto micron range. In sandsand
[GinsburgandSoloviev,1998]. other media with coarsetexture, the segregationcriterion is not
A furtherrestrictionon nucleationof hydratesin porousmedia met even as hydrateenterspore throats,and so accordingto our
(pointedout by an anonymous reviewer)ariseswhenthe gas modelclathratewill continueto grow asan interstitialphase.
supplyto maintainsupersaturation is not strong.This limitsthe At somedepththe mechanicalenergyrequiredfor segregated
amountof methaneavailablein the ambitof smallporesto form a hydrate growth may become greater than the energy saving
critical
nucleus.
Giventher3relationship
between
poreradius
and conferredon the segregatedhydrateby virtue of its small surface
volumeandthe sensitivedependence of nucleationprobabilityon curvature. We speculatethat if early-formed hydrate can flow
the numbersof freely associating
molecules[Adamson and Gast, understresslike ice, it couldbe squeezedinto smallerporesas it
1997],it seemsthatporesizecouldexerta very strongconstraint is buried in the sedimentpile. Over time, it is possiblethat an
on nucleationeven when the pores are much larger than the annealingprocesscouldoccurwherebysmallhydratecrystalsare
criticalsizefor homogeneous
nucleation. dissolvedpreferentiallyto be redepositedas segregatedmasses
Experimental
observations
of shortinductiontimes[Yousif [Everett, 1961]. Yardley [ 1975] discussessucha mechanismfor
and Sloan,1991;Makogon,1981;MelnikovandNesterov,1996], the formation of segregatedmineral veins that grow at the
togetherwith the arguments just outlined,suggestto us that expense of a finer groundmass.The equation describing the
heterogeneousnucleation
in largerporespaces is thenormwhen chemical
potential
of themineralgrain(btm,
grain)
is
gashydrategrowsin poroussediments androcks.
•m,
grain
=•m,bulk
+•mYm,a
[dA
•, • +(We
dV} +Wp) (13)
6.5. ProgressiveGrowth of Gas Hydrate
in Porous Sediments The first term on right-handsideis the bulk chemicalpotentialof
the substance(unstrained,no surfacecurvature).The secondterm
After nucleationthe hydratecrystalwill go througha periodof is a positive free energy contributionarising from surfacearea,
rapid growth. If local equilibriumprevails and methaneis where V,nis themolarvolume,Ym.,theinterfacialenergyperunit
continuallyreplenished,then hydratewill continueto form, area (or surface tension) of the mineral with respect to the
almostuninhibited,and fill any largerporesor fracturesalready surroundingfluid phase,here denoteda. The terms wp and We
presentin the sediment.After this period,the crystalswill are plastic and elastic strain energy terms for internal crystal
impingeon the porewallsandnecessarily adoptgreatersurface strain and reaction against the confining stresses of the
curvatureas intersticesare filled and smallerthroatspenetrated. surroundingsediment.If hydrate is like ice we can probably
According to (11), this restricted growth stage requires neglect internal strain energy [Everett, 1961], so that (13) is a
progressivelygreater supersaturation,from cooling or an thermodynamicbalance reflecting the mechanical equilibrium
increasedmethanesupply. expressedby (12). Together these can be used to relate the
Considerthe following scenariowith referenceto the phase mechanicalforces mobilized by a growing curved crystal to the
diagramshownin Figure8. For smallamounts of gasdissolved in thermodynamic drive available from undercooling and
the water(to the left of the field markedL) no hydratecanform. supersaturation.
As the amountof methaneoriginally presentin the pore water
increases,hydrateformsfirst in the largestpores,in equilibrium 6.7. Role of Free Gas
with a fluid stronglydepletedin methane.After equilibriumis
If sufficient methane is present in the system to exceed
establishedat a particulardepth, more methaneenteringthe
solubility in the pore water (compositionsstartingin the L+G
systemwill at firstconvertdirectlyto hydrate,butthenbuildup
regionof Figure8) then free gaswill be presentat and belowthe
in theporewateruntilthesupersaturation is sufficientto drivethe
phaseboundary.It is alsopossiblefor gasto be presentas a stable
hydrateintosmallerandsmallerpores.
or metastablephasewithinthe zoneof gashydratestabilityunder
6.6. The SegregationCriterion and Role of in Situ Stresses certain circumstances.As explained by Zatsepinaand BufJ•tt
[1998], free gas can exist even on the water rich side of the
When the spacein all voidslargerthan a certainsize is filled,
hydratebulk composition if the porewateris sufficientlysaline;
the hydratewill tend to grow as a displacive inclusion or a thishydrate+ liquid+ gasstabilityfield is shownasthe shaded
segregatedlayer ratherthanpenetratinginto smallerand smaller trianglein Figure 8a. Water depletion(and accompanying salt
pores(Figure9). The mechanical conditionfor segregated growth buildup) in a partially closed systemcan move the fluid
is metwhenthephasepressure exertedby thehydratePh exceeds compositionfrom the normal hydrate+ liquid field into the
theeffectiveconfiningstress(o0) plusthe tensilestrengthof the H+L+G field. The baseof the hydratezone will then containa
sediment(Es).It is givenby [cf.Scherer,1993]: depthintervalwhereall threephasescancoexist.In a traverse
throughthe threephaseregion,the hydrateproportionincreases
Ph,seg
--Pw
+Yhw(Ke
-Kp)>rlo+Es (12)progressivelyupwards.
whereKp is the surfacecurvature
of theexistinghydratein the The interfacialenergyof water with methaneis around70-72
porebodiesand K e is the curvaturerequiredfor the nextsmallest mJm-2[TissotandWelte,1978].If hydrate hasproperties similar
throat to be penetrated.The effective confining stress is toiceitsinterfacial energywithwaterwillbearound 30mJm'2.
somewhatlessthanthe verticallithostaticstressat a particular The internalpressureinsidea hydratecrystalliteof radius0.1
depth, as it depends on the stiffness of the sediments and will thenbeapproximately 2 x 3 x 10-2/ 1 x 10-7m = 600kPa
 22,996 CLENNELLET AL.: GAS HYDRATESIN MARINE SEDIMENTS,1

Pw = porewaterpressure
(•'o = effectiveoverburdenpressure
Ph = hydratephasepressure Grains move apart,
nodulegrowswith
reduced surface curvature
(a)

At equilibrium:
Ph = Pw+ Pcap,hyd- (•'o Aqueous
phase
•/•pw
continuous and
at hydrostatic
pressure

Hydrate phase
loaded by
sediment
overburden

•!i??:
..............
• Hydrate inlarge
pores:capillary
'• squeezed
into pressure
negligible
smaller pores,
(b) Pcap,hydincreases

Figure 9. Explanationof gashydratesegregation. (a) Hydrategrowsas an interstitialphasewhen it can adopta

stablesurfacecurvaturethat allowsit to penetrateporethroats.When this curvatureis greaterthana certainvalue
(i.e., all porethroatsgreaterthan a criticalsizehavebeenpenetrated), thenthe hydratepushesasidethe sediment
grainsandgrowsdisplacively. Thishappens whenthe surfacecurvatureenforcesa phasepressure insidethe solid
that exceedsthe yield strengththat can be mobilizedby the sedimentmatrix.(b) Relationshipbetweenlithostatic
load,poresizeandhydratephasepressure. The lithostaticpressure
of overlyingsediments is shownschematically
asa weightpushingdownon the segregated hydrate.At equilibriumthe crystalgeneratesa higherinternalpressure
to balancethis force,enablingit to adoptgreatercurvatureandextrudeinto smallerpores.Circumstance illustrated
wheregasbubbles,havinghighersurfaceenergy,occupylargerporesthanhydratecrystals;the segregation process
itself is not dependenton free gasbeingpresent.

greaterthanthe surroundingporewater,while a gasbubbleof the
samesize would have a capillarypressureof 1400 kPa. Gas will
thereforetendto occupylargerporesin the three-phasezone,and
the phaseswill reconfigureto minimizethe total surfaceenergy
(Figure 10).
In the marine subsurfacewe have assumedthat the liquid
phaseis continuousand wettingto the sedimentgrainsandthat its
pressureis hydrostatic.The gaspressureexceedsthe coexisting
water pressureby an amountthat dependsuponthe size of free
gas bubblesand/or the curvatureenforcedby their confinement
insidepores.At thermodynamic equilibrium,the requirementfor
the chemicalpotentialof dissolvedmethaneto equalthat within
small bubbles of the gas phase leads to an increase in the
concentrationof methanein water. This effect, which has been
discussed by Kamath and Boyer [1995],Claypool [1996] and
Makogon [1996], is termed capillary supersaturation. The
thermodynamic potentialsof the variouschemicalcomponents
changeaccording to the internalpressuresof thephases thatthey
arein (interfacialcurvatureof the bubbleandgasfugacityinside
it are relatedby the Kelvin equation),so changesin the gas
capillarypressurewill influencethe hydrate-formingreactions.
Methane supersaturation promoteshydrateformation,that is, it
counteracts the capillaryinhibitionof hydratein pores[seeHenry
et al. this issue].
 CLENNELLET AL.: GASHYDRATESIN MARINESEDIMENTS,1
Hydrate Water
Figure 10. (a) Distributionof coexistinggas,hydrateandwater
in pores at thermodynamicand capillary equilibrium for a
framework-supported sediment.We assumethe water has an
affinity for the solidsurfacesandis completelywetting,andthat
the gasphaseis completelynon-wettingto pore surfaces.The
hydrateis assumedto behavelike ice andto be completelynon-
wetting,
butwith7hw< 7gw. In orderthatcapillary
forces
balancein a circuit aroundphaseinterfaceswe find the relation:
7hg= 7gw+ 7hw.Under
these
circumstances
thedistribution
of
phaseswhen they are able to coexist(i.e., at thermodynamic
equilibrium)will be arrangedso that water formsa continuous
film on the pore walls, and the highest energy interfaces
betweengas and solid clathrateare completelyavoided.The
configurationshownrepresents a critical hydrateproportionin
thispore(a stabilitylimit). Furthergrowthof the crystalwould
meanan increasein the gasbubblecurvaturethatwould leadto
furthergas dissolution,and disappearance of the bubblefrom
the pore,while the largerhydratecrystalbecomesmore stable
due to lower surfacecurvature,and can acceptmore gas from
solution.That is, the subsystem jumps from a statewherethree
phasesare stable, to one where only hydrate + liquid can
coexist.Basedon Miller, [ 1980].
6.8. Importance of the Total Amount of
Methane in the System
Large changesin the proportionof methanepresentin the
starting compositionwill move the system between different
fields in the bulk stability diagram (Figure 8a), producing
different historiesof phasecoexistenceas the fluid is cooledor
warmed.Only in relativelymethane-rich fluidswill free gasever
appear,while for startingcompositions rich in both gasand salt,
coolingwill involve a traversethrougha regionof three-phase
coexistence beforethe hydrate+ liquid divariantfield is reached.
Confinement in a porous medium adds complications.In a
sedimentwith a distributionof pore sizes, the pressureinside
growing inclusions of either gas or hydrate will rise as the
22,997
percentageof pore spacethat they occupy increases.Thus the
internal pressures of gas and hydrate are a function of
temperature, pore-sizedistribution,andthe startingcomposition,
not just depth below sea level. Reactionsdepend on phase
pressures,so rearrangements may be necessaryfor the systemto
maintain both thermodynamicand mechanicalequilibrium as
hydrategrowsor melts.
It is possiblethat even in the binary system CH4-H20 the
phaseboundary ceasesto be a univariant line and becomesa
divariantregionwhere gas+ liquid + hydratemay be stable.An
extra degreeof freedom,namely, phasesaturation,is introduced
into the system.The behaviorparallelsthat of the ternarysystem
with salt present,but in the capillarycasethe increasedvariance
comesnot from an increasein the number of componentsbut
from the fact that the gas pressureno longer has to equal the
water "reference"pressure.Figure 8b is an attemptto sketchthe
T-X sectionof the binary system.
Where there is a three-phase stability zone, the first
appearanceof free gas bubbleswhen goingdownwardsinto the
sedimentneednot in generalcoincidewith the lastappearance of
hydrate,even when the salinity is not unusuallyhigh. The first
appearance of gas,and so the positionof the bottomsimulating
reflector, will dependuponthe level of capillary supersaturation.
This in turn will be a functionof the pore-sizedistributionin the
host sedimentand the total amountof gas in the system.Thus,
accordingto our model,the BSR couldbe encountered at various
depthsin the samesedimenttype accordingto the amountof
methanepresentat that locality.
Capillary pressure-saturation curvesfor sedimentsinvariably
exhibit hysteresis:pore bodies are linked by narrow throats
[Griffithsand .]oshi, 1989;Jallut et al., 1992]. This impliesthat
differentconditionsof phasesaturation,pressure,andtemperature
will prevail in the three-phasezone dependingon whether,over
time, the baseof hydratestabilityis movingup or down relative
to the sedimentarystrata, and this will affect the BSR position
[seePecheret al., 1998].
We now consider the possibility of overpressurein the
referencepore fluid causedby compactiondisequilibrium,high
basal fluid flux, or some other mechanism.An increase in water
pressure abovehydrostatic will leadto an similarincreasein the
gasphasepressure in orderto maintaincapillaryequilibrium.The
chemicalpotentialof the methanecomponent thusincreaseswith
the rise in the pore water pressure,so promotingthe forward
reactionto producehydrate,even if there is no increasein the
total amountof methane[Handa, 1990]. The volumeof hydrate
neednot necessarily riseproportionately asthis happens,someof
the methanesqueezedout of solutionmay go to increasethe
percentage occupancy of gasin thehydratelattice.
6.9. Hydrate Growth in a Partially ClosedSystem
and SedimentWater Depletion
Growth of hydratein concentratedlayersor in noduleswill
sequesterwater and gas from surroundingsedimentsin a way
analogous to ice lensesin frozensoils[Miller, 1980; C/ennellet
al., 1995]. The effect on the surroundingsedimentsdependson
the speedof hydrategrowthrelativeto the ratesat which water
and gas are suppliedby transportthroughthe sedimentand the
excludedsalts are diffused away [see Usslet and Paul/, 1995].
Hydrate growth rate will also dependon heat transfer, but
considering
thatthediffusion
of heat(typically,
l0 m2yr'•) is
about 500 times faster than diffusion of either salt or methane
(typically,
0.01-0.02m2yr-•) [Iversen
andJorgensen,
1993],salt
buildup
islikelytobethelimitingfa?ror.
 22,998 CLENNELLET AL.: GASHYDRATESIN MARINE SEDIMENTS,1

We speculatethat where the permeabilityis low and gas seafloor at which hydrate is first encounteredand reduce the
supply(in situ microbialproductionplus influx) is high, there amountof methanepartitionedintohydrateat anydepth.
will be a thermodynamicdrive to draw pore water from 3. (a) Formation of segregatedhydrate in fine-grained
surrounding sedimentsat a rategreaterthanit canbe replenished. sediments,and interstitialhydratein coarsersedimentlayers.(b)
This "suction"on the pore fluid will increaseeffectivestressand Suppressionof this tendencyat greaterdepthwhere overburden
lead to consolidationthe sediment. Konrad and Duquennoi pressuremay squeezehydrateinto smallpores.
[1993] explain sucha processwhen ice segregates duringsoil 4. With a partly closed-system or high gas flux: (a) Water
water freezing, though we appreciatethat the analogy is not depletionin the vicinity of concentrated hydrates.(b) Haloesof
perfect because in the case of clathrate growth the water is salinewater aroundgrowinghydratedue to incompletediffusion
probably sequesteredbecauseof local gas excessrather than of excluded salt.
through thermodynamicundercooling(G. Ginsburg personal 5. Freegaspocketswithinwhatwouldnormallybe thehydrate
communication, 1998; A. Rempel personal communication, two-phase region. These may be detectablefrom low sonic
1998). Cores recoveredfrom a water-depletedsequencemay velocitiesandseismicblanking.
showmarkedexcursionsin physicalpropertiesbetweendry and 6. (a) Hysteresisin the physicalconditionsof gashydratefirst
stiff water-depleted horizonsand anomalously wet layers(soupy and last appearanceduring formation and melting in the
or moussytexture)wherepreexistinggashydratehadmelted. sediment.(b) Differentphaseproportions at a giventemperature
Ginsburgand Soloviev [1997] stressthat advectionof pore and pressurein the three-phaseregion accordingto whetherthe
water containingdissolvedgasandtransportof methaneas a free sediment mass is moving, relatively, into or out of the
gas phaseare fundamentallydifferent scenarios.In the former thermodynamic regionof clathratestability.
case water is supplied along with the gas, and hydrate
precipitationis somewhatakin to freezingof a water stream.In
7. Discussionof the Capillary Model
the latter case,gas is in excessof its proportionin hydrateand
water must be drawn from the surroundingsfor the reactionto 7.1. Unknown SurfacePropertiesof C!athrates
proceed.In mud volcanoesor otherareasof focusedgasflow, the
There are no reliable publishedvalues for the interfacial
sedimentaroundthe gas pathwaysmay becomedried out and
energyof hydrate;nucleation phenomena areverysensitiveto the
lined with hydrates.This "frozen" barrier allowsthe passageof
exact value of surfaceenergy [Davis, 1996]. Recentmolecular
moregasthroughthe conduitwithoutit combiningwith waterto
dynamicssimulations revealthatournotionsof interfacialenergy
form clathrates[GinsburgandSoloviev,1997].
and wettabilityare a simplificationof a rathercomplexsystem
We speculatethat in extreme casesof "freeze drying," the
[Rodger et al., 1996; P.M. Rodger,personalcommunication,
residual water may be present only as capillary water in
1996 and 1997]. Nevertheless,experimentson the criticalsizeof
intersticesor as films adsorbedon sedimentparticles.The low
hydratenuclei in aqueoussolution[Higskoleet al., 1994] and
chemicalpotentialof this residualwater (Figure5) may prevent
structural considerations both suggest that the effective
its reactionwith gas to form more hydrateunderthe prevailing
hydrate/waterinterfacialenergyis similarto that of ice (Y. P.
conditions. Through this water depletion mechanism,small
Handa, personalcommunication,1995 and 1997; K. Lekvam,
quantitiesof free gas may be trapped in dry, hydrate-bearing
personalcommunication 1996),andwe usethisvaluehereandin
sediments, perhaps leading to seismic blanking or locally
thecompanion paper[Henryet al., thisissue].
affecting the seismicexpressionof the BSR. If salt builds up
duringthis "gasflushing,"a fringeof brinemay surroundpatches 7.2. Effects of Host Sediment Surface Chemistry
of hydrate, and this would draw in water osmoticallyfrom
surroundingsediments[Mitchell, 1993; Konradand Duquennoi, Cha et al. [1988] andsubsequently Ouar et al. [1993] reported
1993]. The moreactivea methaneventingsystemis, the fi,•rtherit that clay suspensions canpromotethe rateof hydrategrowthand
can be pushedfrom equilibrium. For example, the water and its equilibrium thermodynamic stability relative to bulk
solute contents of the sedimentssampled from active mud conditions.However, experimentsconductedby Englezosand
volcanoesmay be very heterogeneous [de Langeand Bruinsack, Hall [1994] found no enhancedeffect from montmorillonite
1998]. surfaces and confirmed the finding that most organic and
The amount of gas necessary for water depletion is inorganicmaterialsactedto inhibithydrateformation.While it is
considerable. To dry a sedimentof 50% originalporositydownto possiblethat certainmineralsurfacescanpromoteheterogeneous
the point where all the water is boundto particlesurfaces(say nucleationof hydrate,it is lesscertainthat they can increaseits
10% water content)requiresremovalof 400 kg of water,and so a thermodynamic stabilitysignificantly.Carlisle [1983] suggested
supply of nearly 75 kg methane, for each cubic meter of thathydratenucleationwouldbe favoredby partialpreordering of
sediment.For a sedimentorganiccarboncontentof 1% that is water moleculesinto tetrahedralcoordinationadjacentto strongly
convertedto methaneby bacteria with 10% efficiency [e.g., hydrophobicsurfaces.Most mineralsfoundin marinesediments
I4'aseda,1998], the amountof methanerequiredfor drying is arehydrophilic, butthemis someevidencethatorganicsubstrates
about50 timesgreaterthancouldbe suppliedin a closedsystem. such as kerogens or biofilms may possibly promote hydrate
precipitation.
Van Kesteren and others report that anomalously large
6.10. Predictionsof the Capillary Model
amountsof propanewill dissolvein clay slurriescomparedwith
Our conceptualmodelpredictssix main phenomena that can the solubilityin water at the sameP and T; hydrateformation
be testedby observationsof naturalgashydratesystems: appearsto be promotedalso. This is interpretedeither as
1. Upwardsdisplacement of the BSR in fine-grainedsediments adsorptionof gas moleculeson the mineral surface and/or
due to inhibition of hydrate nucleation and growth. In the capillary supersaturation (W. G. M. van Kesteren, personal
companionpaper,Henry et al., [thisissue]quantifythiseffect. communication, 1998). It is not clearhow similarthe behaviorof
2. Capillary inhibition will increasethe depth below the methanewouldbe to the largerpropanemolecule.
 CLENNELL ET AL.: GAS HYDRATES IN MARINE SEDIMENTS, 1 22,999

7.3. Controls on Gas Hydrate Growth Forms processof continuousmelting, upwardstransportof gas, and
recrystallizationat a higher level [seeHyndmanet al., 1992,
The development of facetedratherthancurvedcrystalfaces
Brown et al., 1996].
(implicit in our model)is likely for crystallitesabovea few
micronsin size [Adamsonand Gast, 1997], but the qualitative Concretions typically exhibit diffusion-limited growth,
behaviorwe describewill be the same so long as the clathrate whereby isolatednucleidepletethe surroundingporewatersof
growthformsremainconvexandcompact[seeEverett,1961]. the mineral constituents
andthismaterialis replenished
through
relativelyslow diffusivetransport[Cody, 1991;Selles-Martinez,
Compactgrowthhabitsareoftenfavoredwhena mineralgrows
slowlyfrom solutionat a low degreeof supersaturation [Cody, 1996].Norvikand Lekvam[1994] usedthismodelto explainthe
1991;B. Yardley,personalcommunication, 1996]. Suchforms distributionof hydratepatchesgrowingin submarinesediments,
were observed recently in Structure I methane clathrate andthe samereasoningpredictsthat largenodulesor lenseswill
be spacedthroughoutthe sediment.
crystallites
by SmelikandKing[ 1997].
Takingthe availableobservations at face value, it would
7.4. Thermodynamic Degreesof Freedom and Phase
appearthat massiveor "segregated" hydrategrowth forms
Stability in Porous Media
predominate in fine-grained
sediments,
butthatsometimes fine
sedimentscan host clathratesthat are widely distributedand Incorporatingcapillarypropertiesinto the descriptionof the
"diffuse"in the sediment(e.g., Blake Ridge and CostaRica hydratesystemchangeshow we canapplythe Gibbsphaserule
Margin).We notethat fine-grained sediments predominate
in as a meansof predictinghow many phasescan coexistin stable
deepmarineenvironments andthatmosthydratesmnples that equilibrium[Gaydoset al., 1993]. The usualstatementof Gibbs
survivethroughcore recoveryto the time of inspectionwill phaserule foundin textbooksis
necessarilybe biasedtowardthe largermasses.On the other
F = NC- NP + 2 (14)
hand,apparentlydiffusehydratein fine sediments may in fact
consistof small nodulesor inclusions(10 •xmto 1 mm across). NC is thenumberof independently actingchemicalcomponents,
Althoughinvisibleto the nakedeye,thesehydrateparticlesare and NP is the numberof stablephases.F is the varianceor
considerablylargerthantheporesandso,in termsof ourmodel,. numberof degrees of freedomof thesystem, whichis a statement
havea segregated
habit. of the numberof variablesneededto completelydefine the
The capillarymodel predictsthat deeperin the sediment system minus the number of independent equations that
column,hydratecouldbe squeezedinto smallerpores,with interrelatethem.Theseequationsare Gibbs-Duhemequationsof
nodulesexhibitingthe effectsof pressure solution.This typeof the form of (5) writtenfor eachof the NP phases.The number2
behavioris evidentin sediment-hosted anhydritenodules[Machel refersto the numberof non-compositional variablesrequiredto
and Burton,1991]. The looseanalogybetweensulfateminerals describethe stateof the system,which for bulk systemsare the
andgashydratenodules is promptedby theirremarkably similar intrinsic properties of pressure and temperature. If all the
appearance, at leastat the scaleof handspecimens (compare chemicalandphysicalvariablesof the systemarespecified, there
photographs in Peyrtet al. [ 1993],with[Sloan,1990,p. 411] and is no variancein the system(this statewill be a singlepointon a
Kvenvoldenet al., [ 1993]). phasestabilitydiagram),whereasif oneparametercanbe varied
Kastner [ 1970] and Shearman [ 1981] studiedthe factorsthat freely without influencing any others, we have a univariant
control whether gypsum crystals grow to envelop sediment condition,andsoon [Fletcher,1993].
particles,so forminga poikilotopiccement,or alternativelypush In capillarysystemsat thermodynamic equilibriumwe note
sedimentparticlesasideduringgrowth.Rapid growthwas found thatchemicalpotentials of individualcomponents mustbe equal
to favor overgrowth, whereas slow growth favors particle in all phases, andtemperature mustbe uniformacross thesystem,
displacement and segregation:clearlythe force of crystallization but pressurescan changeacrossthe curved interfacesbetween
thatcanbe mobilizeddependspartlyon kinetics,notjust on pore phases.Whenthe configuration of differentphasescan change
size. Studieson the growthof ice in a matrix of silica particles freely to adopt a minimum energy conditionwithoutmechanical
reportedby Scherer [1993] also demonstratethat crystalswill constraint, the Gibbsphaserule becomes
engulfratherthanpushasideparticleswhengrowthis rapid.This
occursat negligibleeffectiveconfiningstressesand despitethe F = NC + 1 (15)
fact that ice is strongly nonwetting to silicates. The critical [e.g., Nitao and Bear, 1996]. For each additionalmechanical
growth speedis determinedby the rate at which water can be constraint condition,oneof thephasepressures will be eliminated
transportedinto the gap betweenthe face of the crystaland the from the total variance[Li and Neumann,1994].In a porous
displaced particle.We speculate that interstitialformsof hydrate mediumwherewater is a completelywettingphase,sucha
may attestto relativelyrapid growth,and so a high degreeof constraint condition appliesbecausethecontact angleat thepore
undercoolingand/or supersaturationof the pore fluids with wallis fixedat 0ø.Thefractional proportions of eachphasein the
methane.In contrast,nodularformsof hydratemay suggestthat porous mediummustsumto 1, andonlycertainconfigurations of
the nucleationof hydrateand its rateof growthhavebeenreduced phases in the porespacecan satisfymechanical equilibrium
by inhibitors [Cody, 1991], restrictedtransportof reactants (Figure 10).
[Putniset al., 1995], or slowproductionratesof methane. Whilethe detailedthermodynamics of capillarysystems are
Several authorssuggestthat annealingduringmelting and beyond thescopeof thispaper,we canmakesomeusefulpoints.
recrystallizationcycles may be important in concentrating First,the numberof phasesthat can coexistinsidea porous
hydratesinto particularlayers[Malone, 1985; YousifandSloan, mediummay differ fromthatexpected for an equivalent bulk
1991].Suchannealingcanoccurin the shallowsubsurface during system.Second,the mobilephasesinsidea porousmediumwill
uplift/burial or glacial sea level and sea bottom-temperature rearrange into a configurationthat hasa local surfaceenergy
changes[Whiticaret al., 1995] (seebelow),andat the baseof the minimum:thisis not a globalfreeenergyminimum.Transitions
stabilityzone the hydratecouldbe progressively enrichedby a betweenstablestatesmay proceedin a discontinuous manner,
 23,000 CLENNELLET AL.: GASHYDRATES1NMARINE SEDIMENTS,1

with abruptjumps in saturationand phasepressures[Gaydoset and the residualpore spaceis diminishedby overconsolidation,
al., 1993; cf. Miller, 1980]. Third, thermodynamic so that calculationsof the amountof hydratewithin a particular
transformations
in porousmediawill exhibithysteresis.Finally, depthintervalmay be underestimates.
the thermodynamic stateof a phasewill dependon its capillary Current estimatesof gas hydrate volumesmade on a more
pressure,which is determinedby the pore size distribution, regional scale are based upon values of seismicvelocity and
surfaceenergy,wettability, phasepercentages and, becauseof reflectivitycalculatedrelativeto normallycompactingsediments
hysteresis,thesaturation
history. [Leeet al., 1993; Woodet al., 1994; •4ndreassenet al., 1995]. It is
appreciatedthat suchestimatesare sensitiveto the assumptions
7.5. Elevated BSRs: Inhibition or Disequilibrium? made regarding how the hydrate is distributed within the
sediment [Dvorkin and Nut, 1993; Anderson, 1994].
At ODP sites 889 and 892 the thermal profiles derived from
Observations from Leg 146 and elsewhere [Ginsburg and
downholemeasuringtechniquessuggested thatthe temperatureat
Soloviev,1997] would suggestthat the physicalproperties,and so
the BSR is too low for it to correspondto the bulk equilibrium
the seismic response, of sediments adjacent to hydrate
positionof the methanehydrate-seawater system; thatis theBSR
concentrationsare modified by water depletion. Such over-
is anomalously shallowby a t•w tensof meters[Whiticaret al.,
consolidatedsedimentswill have increasedvelocity and the
1996]. However,longer-termmeasurements reportedfrom the
reflectivity of interval boundarieswill be affected.It is not yet
instrumentedHole 892B show that, within error, the positionof
clear whetherthe mechanismswe invoke for segregatedhydrate
the regionalBSR is in line with the seawater-methane hydrate
growthwould lead to gas hydratevolumesbeingunderestimated
curve[Daviset al., 1996].Therefore,the localmismatchof the
or overestimated,but we caution that the responseof the host
BSR depthon the verticalseismicprofile and soniclogs,with
sedimentaddsan extradegreeof uncertaintyto calculations.
respectto the temperatureprofile at Site 892, may havebeena
transient feature associatedwith drilling disturbance(perhaps
eithergas migratedupwardsor cold drilling waterenteredthe 8. Summary and Conclusions
formation).
We suggestthat as a result of capillarity and osmosis,gas
During ODP Leg 164, thermalprofilesthroughsiteson the
BlakeOuterRidgerevealedan evenlargerdiscrepancy in depth hydrate will be distributed heterogeneouslyin a sequenceof
to the BSR, which lies 30 to 100 m abovethe expectedposition sedimentsaccordingto textural and mineralogicalproperties.
of thebaseof hydratestability[Paull et al., 1997;Ruppel,1997]. Segregated growthformsare likely in fine sediments,
particularly
in the near surfaceand where growthratesare modest.Interstitial
These discrepancies are minimumestimatesbecausethe pore
watersat depthare freshetthan seawater,andtracesof higher hydrateis favoredin coarsesediments andmay be moreprevalent
at greaterdepth,or wherethe reactionto form hydrateprogressed
hydrocarbons, CO2,andhydrogensulfidemay alsostabilizethe
rapidly. Our model is consistentwith data availableon sediment
hydraterelativeto thepuremethanebenchmark. It is possible
that
the displacedBSR on the Blake Ridge is the result of texture,poresize,andhydratedistribution.
disequilibriumarising from changesin sea level and water In fine-grained sediments, the hydrate phase may be
temperaturesincethe lastglacialmaximum[seeWestbrook et al.,destabilizedthermodynamically,and perhapsinhibited from
1994].Mieneftand Posewang[ 1997]reporta second,metastable nucleating, untilthe prevailingtemperatureis considerably
cooler
BSR in an area of slumpingon the Norwegianmarginthat has than the bulk equilibrium value, perhapsby as much as 0.5ø to
persistedfor thousandsof years. However, Ruppel [1997] 3øC. This is sufficientto displacethe BSR upwardsby several
discountedthis possibilityas lesslikely for the Blake areathan tens of meters relative to predictionsbased on bulk stability
some kind of inhibition due to the environment within the marine equilibriumcurvesand will increasethe depth of first hydrate
sediments.Most recently,Xu and Ruppel[ 1999] havearguedthat appearanceby a similar amount. These estimatesare basedon
the offset in the positionof the BSR can be explainedas a publishedexperimentaldataandby analogywith ice formationin
consequence of upwardsflow of fluidsand heat.We suggest soils;precisecalculationsof the capillaryeffectsare given in the
somepossiblemechanisms that coulddisplace the BSR even companionpaper[Henry et al., this issue].
whenconditions of quasistaticequilibrium prevail. We speculatethat wherethe local influx or in situ production
The factthatthe baseof gashydratestabilityshouldoccurat a of methane is great, water depletionand strongcapillaryforces
predictabletemperature for a givendepthhasbeenusedasa way may act to stabilizeisolatedpocketsof free gas well abovethe
to estimatethe heat flow where BSRs are visible on seismiclines normalbaseof hydratestability.This may explainoccurrences of
[Hyndman et al., 1992].If theprominent
reflector
markingthe anomalously lowseismic velocity(lessthan1.5kms-1)withinthe
top of freegasis coolerthanthatpredicted by bulkstability hydrate stability zone at continental margins [Fontana and
conditions, usingthisassumption Mussumeci, 1994; Rowe et al., 1995]. Certain instancesof
thenheatflow valuescalculated
will be overestimates. markedseismicattenuation(blanking)that are not accompanied
by a commensurate increasein sonicvelocity [Woodet al., 1994;
7.6.Implications
for Estimatesof GasHydrateVolumes W. Wood personalcommunication, 1998], and so are not easily
explicablesimply as zonesof hydrateprecipitation,may alsobe
The volume of hydrate present in sedimentshas been relatedto changesin sedimentphysicalpropertiesduringwater
estimatedfromthe degreeof freshening
as indexedby chloride depletion.We suggestthat estimatesof gas hydrateabundance
depletion
[HesseandHarrison,1981]in porewaterssqueezedbaseduponseismicor otherindirectsensingmethodsshouldtake
from sedimentsrecovered from hydrate-bearingintervals. into accountpossiblehostsedimenteffects.
Hydratevolumeis calculated
frommassbalanceassuming a
startingporewatercomposition
anda likelyporosityfor the Notation
sediment.Our model predictsthat hydrate is likely to be
concentrated
in segregated
massesthat draw water from the g acceleration
duetogravity,
ms'2.
surrounding
sediments. In this water depletionscenariothe h waterdepth,m.
hydrate
doesnotinhabittheoriginalporespace of thesediment,z depthbelowseafloor,m.
 CLENNELL ET AL.' GAS HYDRATES 1NMARINE SEDIMENTS, 1 23,001

F1 firstprincipalradiusof curvature,m. References

/'2 secondprincipalradiusof curvature,m.
Adamson,A.W., and A.P. Gast,PhysicalChemistryof Surfaces,6th, Ed.,
effective, cylindrical-equivalent
radiusof curvatureof 784pp.,JohnWiley, New York, 1997.
porethroat,m. Anderson,A.L., Discussionrelated to papersby Dillon et al., Brookset
actualradiusof curvatureof porethroat,m. al., and Paull et al., Ann. N.Y. Acad. Sci., 715, 410-411, 1994.
Andreassen, K., P.E. Hart, P.E. and A. Grantz, Seismic studies of a
effectiveradiusof curvature
of porebodyof actualradius
bottom simulating reflection related to gas hydrate beneath the
rp, m. continentalmarginof the BeaufortSea,d. Geophys.Res., 100, 12659-
presentradiusof curvatureof poreice,m. 12673, 1995.
/"crit minimumradiusof curvatureto forcesegregated
crystal Bondarev, E.A., A.G. Groisman, and A.Z. Savvin, Porous medium effect
growth,m. on phase equilibrium of tetrahydrofuranhydrate,paper presentedat
Second International Conference on Natural Gas Hydrates, United
surface
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