1

GES166/266,SoilChemistry

LectureSupplement1
SoilSolids

SOILMINERALOGY
I1,MineralStability
Mineralswillbothdegrade(dissolution)andform(precipitation)duetometa
stableconditions.Wecanbreakthemineralsintotwoformationcategories:PRIMARY
& SECONDARY. Primary minerals are formed at high temperatures and pressures
throughwhatwemaytermgeologicprocesses.Consequently,theyareunstableunder
atmosphericconditions.Secondarymineralsformunderatmosphericconditions(suchas
those found in soils) but may be unstable if conditions change from those of their
formation.Primarymineralstendtoreleasetheirionicconstituents;thiscanleadtothe
"neo"formation(i.e.,precipitation)ofsecondaryminerals.Secondarymineralscanalso
beformedfromthesolidstatetransitionofaprimarymineral,e.g.,mica>vermiculite.
The formation conditions of primary minerals leads to their stability, and is
summarizedbytheBowenReactionSeriesshownbelow. Thisseriesstartswiththe
minerals formed at the highest temperature with subsequent minerals formed at
progressivelylowertemperatures. Thestabilityofthemineralsinsoilsincreaseswith
lowertemperaturesofprimarymineralformed.

BowenReactionSeries
Olivine
Ca-Feldspar

Least
Stable

Augite
Hornblende

Na-Feldspar

Phlogopite
K-Feldspar
Muscovite
Quartz

Most
Stable

I2,IonBonding:Aquickreview
Ionsormoleculesaggregateinresponsetoelectrostaticandchemicalattractions. The
interactionstrengthdependsonthetypeofbond,whilethecoordinationnumbersdepend
ontheratiosofionormolecularsizes.
TypesofBonds:
Ionic:bondsthatoccurbetweenionsofoppositechargewithoutthesharingof
electrons.
occurbetweenelementsonoppositeendsoftheperiodictable
nondirectionalbonds
relativelystrongbondsgivinghighmeltingpoints
verycommonforsoilmaterials,e.g.,NaCl,CaCO3,etc..
Covalent:thesharingofelectronpairsbetweenthecombiningatoms
occurbetweenatomsofsimilarelectronegativity,e.g.,H2O,CH4
strongestbond
directional
bondingwithinmoleculesisusuallycovalent

3
Hbonding: aweakelectrostaticbondbetweenH+ andhighlyelectronegative
atoms,e.g.,F,O2.
although weak individually, they can be very strong when
multiplied
waterformsHbonds
vanderWaals:weakattractiveforcesbetweenatoms.Theycanbesignificant
when present in large numbers but generally result in very weak planes of
attraction
Bonding is rarely exclusively of one kind, e.g., in crystals most bonds are a
compositeofbothcovalentandioniccharacter;thedegreeofeachcharacterdoesvary
significantly,however.
TheBondValence()(electrostaticbondstrength)isaconvenientwaytodenote
thechargebalancedbyeachbond.Itistheformalchargeobservedbetweenthecentral
cationandeachcoordinatingatom.
=(cationvalence)/cationcoordinationnumber=Zcation/CNcation
examples:Al(OH)6:=3/6=1/2
OH

-1/2

OH
-1/2
-1/2
OH

-1/2

Al -1/2

OH

-1/2

SiO4:=4/4=1
O
1
1 Si 1
O
1
O
O

I3,IonCoordination

OH

OH

4
Atoms bond to stabilize their electronic configuration or to provide charge
shielding. Wewillcallthecationthecentralion,anditwillbecoordinatedbyanions
thatwewilltermligands.Thecoordinationofacationbyaligandisdependentonthe
ratiooftheirsizesitisstrictlyageometricfactor. Thefollowingtable providesan
estimateofusualcoordinationobservedinnatureforsizeratios.

TableofRadiusRatiosandexpectedcoordination.
RadiusRatio
(rcation/ranion)

Coordination
Type

0.150.225
0.2250.414
0.4140.732
0.7321.000
1

Coordination
Number

trigonal
tetrahedron
octahedron
cube
dodecahedron
(closestpacked)

3
4
6
8
12

Examples:
Hightemp:AlO:RAl=0.51,RO=1.40;RAl/RO=0.364=>tetrahedron
Lowtemp:AlO:RAl=0.60;RAl/RO=0.429=>octahedron
SiO:RSi=0.42;RSi/RO=0.3=>tetrahedron
I4,BuildingBlocksofSoilMinerals
Oxygenisthemostabundant elementintheearth'scrustandisthedominant
elementinthesolidsofsoils.SiisthesecondmostabundantandAlthethird;theyalong
withOmakeupmostofthemineralswewillconsider.WealsoneedtoappreciateMg
sinceitmakesupaclassofmineralswewilldiscuss.
Basicbuildingblockonthemolecularscaleare:
SiO4

Al(OH)6

Mg(OH)6
OH
OH
OH

OH
Mg

OH
OH

OH
OH

Si

O
O

OH

OH
Al

OH
OH

These units can be linking and stacked in various arrangements to give the
commonmineralsweobserveinsoils.Thiscanbethoughtofaseither1)thebuildupof
molecularlinkagesor2)oxygensheetsfilledwithcationsthatareneededforelectrical
neutrality.
Onthefollowingpage,bothoctahedralandtetrahedralsitescanbeseenbythe
arrangementofoxygensheets. Therearetwotypesof'voids'presentintheseoxygen
sheets,whicharedesignatedby'b'and'c'.Duetochargeconstraints,onlyonetypeof
voidwillbefilledinthephyllosilicateminerals.Itdoesnotmatterifitisthe'b'or'c'
typevoidsthatfill,butonlythatthemineralhasonetypeconsistently(exculsively)filled.
Now,basedonelectricalneutralityyoushouldbeabletodeterminetheoctahedralor
tetrahedralcationoccupancy.

Octahedral Cavities,
f ormed when cavit ies
align over cavit ies

b
b
C

Tetradral Cavit ies,

occur when an at om
is placed over a
cavit y

bb
c

7
Theoctahedralvacancieswillbefilledtomaintainchargeneutrality. Wecan
determinetheirfillingbyfirstusingthebondvalencetheory.Fortrivalentionssuchas
Al3+inoctahedralcoordination,=1/2.Therefore,weknowthateachanionwillhave
1/2ofachargesatisfiedbyeachbondtothetrivalentcation.Iftheanions(ligands)are
hydroxyls,asingibbsite[Al(OH)3],theneachOHmustbeboundto2Al3+forcharge
neutrality.Wecanwriteaformulafortheneededcoordinationoftheligandbasedonv:
[Thenumberofcationscoordinatingeachanion]=[(anioncharge)/]
So,foradivalentions,suchasMg2+,inoctahedralcoordinationbyOH[Mg(OH)2]:
v=1/3,and3(1/1/3)Mg2+mustsurroundeachOH.
Infact,thesearetheobservedcoordinationenvironmentsinminerals.Inthediagrams
below the position of divalent and trivalent cations is shown to give the observed
coordination.
= Al

= Mg

Notethateveryoctahedralsiteofthesametypemustbefilledtoobtainchargeneutrality
with divalent cations. For trivalent cations this is not the case; here, every third
octahedralsitemustremainvacantinordertomaintainchargebalance.Thevacantsites
inadjacentrowsareshiftedsothatvacanciesaredirectlybelowtwofilledoctahedral
sites.Takealookatthesediagramsandmakesurethatyoucanseethateachhydroxylis
maintainingchargeneutrality,except,ofcourse,thoseattheedges.Agoodwaytocheck
whethertheoctahedralsitesarefilledcorrectlyistodrawahexagonalringwiththefilled
sites(seebottomdiagramonthepreviouspage).Ifahexagonalringdoesnotresultthen
thefillingwasincorrectlydiagrammed.

FormingandLinkingTetrahedralandOctahedralSheets
Themainclassofsoilmineralsareformedbylinkingsilicatetrahedra,tofrom
tetrahedral sheets, and either Al or Mg octahedra, to form octahedral sheets. The
tetrahedralsheetsareformedbyasharingof3O,whichformhexagonalrings,andgivea
formula(Si2O5)2.Theoctahedral.unitsareMe(OH)2orMe(OH)3(whereMeisametal
cationsuchasAl3+,Mg2+,orFe2+).Theoctahedralsitesintheoxygen(hydroxyl)lattice
canbecompletelyfilledbydivalentcationsortwooutofeverythreesitescanbefilled
bytrivalentcations,aswehavejustdiscussed. Since3outof3sitesarefilledinthe
divalentcationcasethesemineralsaretermedtrioctahedral;thosewithtrivalentcations
aredioctahedralminerals.ItturnsouttheAlandMgoctahedrahaveligandpositions
very closely aligned to those of the apical oxygens in the silica tetrahedra. As a
consequence,thetetrahedraandoctahedracanlinktogethertoformaclassofminerals
knownasthephyllosilicates('phyllo'beingaGreekwordfor'layered').Asshownonthe
followingpage,thephyllosilicates canhavevaryingratiosoftetrahedratooctahedra.
Thesimplestformisjustasingleoctahedra;thenexttypeofphyllosilicatewouldhavea
Sitetrahedralsheetaddedto1octahedralsheet(a1:1mineral).Thenwemoveontoone
composed of 2 tetrahedra and 1 octahedra (known as a 2:1 mineral). The ratio of
tetrahedra to octahedra is the dominant means of classifying the phyllosilicates.
Additionally,thisclassofmineralsisfurtheridentifiedbythecationintheoctahedral
positionandthelayercharge,whichisournexttopic.

Al

Si

OH
gibbsite

Oct .

kaolinite
Tet .

Oct .

{
{
pyrophollite

Tet.

Oct .

Tet .

apical oxygen
basal oxygen

10
I5,ChargeDevelopment
Therearetwoprimaryprocessesbywhichmineralsexertacharge: isomorphic
substitution and terminal ("broken") bonds. Isomorphic substitution is the
replacementofoneionwithanotherhavingadifferentchargebutwithnochangeinthe
mineralstructure.ExamplesarethesubstitutionofAl3+forSi4+orAl3+forMg2+.This
charge is termed "permanent" since it will not vary as a function of the solution
composition. Terminal (broken) bonds result from coordinately unsaturated central
cations or ligands that occur at terminal ends of many minerals. Mineral that are
composedof2dimensionalor3dimensionalgrowthpatternsneedtoextendinfinitelyto
satisfyalltheircharges;thisofcourseisnotpossibleandsothatatthesurfacesofthese
mineralsachargewillemanateintothesurroundingmedia.Insolutionsuchsurfaceswill
reactwithwateranditscomponents(H +andOH)yieldingapHdependentchargethis
isalsotermedavariablechargedsurface.Ofthemineralswewilldiscuss,thexaxis{the
(100)plane)andyaxisedges{the(010)plane}ofthephyllosilicatesandallfacesofthe
hydrousoxideswillhavevariablecharges.
The charges on the functional groups of variable charged surfaces can be
determinedbasedontheknowledgeofthebondvalencesandcoordinationnumber.For
example,supposewearelookingatthemineralgibbsite,Al(OH) 3;Alentersoctahedral
coordination(CN=6),sothat6OH ionsmustsurroundeachAl.WealsoknowthatAl
istrivalent,whichleadstov=3/6=1/2.FromthiswecanalsoreasonthateachOH
mustbeboundtotwoAlionstosatisfyitscharge(eachbondonlysatisfies1/2acharge
andtheOH has1unitofchargesotwobondsareneededtofullysatisfyitscharge).
Therefore,ifatthesurfaceofgibbsiteaOH ionisonlyboundto1Althenitwillhavea
chargeof1/2. Thissurfacegroupcouldalsoreactwithwaterandbecomeprotonated
yieldinga+1/2charge.
mineral

surface
plane

protonation
(occursatlowpH)

positivelychargedsurface

11

OH

OH
Al

OH

-1/2

Al

OH

-1/2

+1/2
OH2
OH

+ 2 H+

OH
OH

Al

Al

+1/2
OH2
OH

12

I6,CrystalPlanesandFaces(MillerIndices)
Inmanyminerals,particularlythephyllosilicates,differentcrystalfaceswillhave
vastlydifferentpropertiesthanothers.Accordingly,weneedtohaveanomenclaturethat
willallowustoidentifythesedifferentmineralsurfaces.Toaccomplishthisweturntoa
notationcalled"MillerIndices".
TheMillerIndexuses3parametersinaCartesiancoordinatesystemtorepresent
afaceorplane.Planesandfacesaredesignatedby:(hkl).Inthissystem,hklrepresents
thereciprocalofthespecificaxisintercept,wherehisforthexaxis,ktheyaxis,andl
thezaxis.Furthermore,theMillerIndicesarealldesignatedtobewithin1unitvalueof
eachaxis.Why?Becauseforanymineralthelengthgivenby1unitvalueisthatofthe
unitcell (thesmallest repeatable unitwithinthecrystal). Sincetheunit cellcanbe
repeatedtomakeupthecrystal,movingtoasecondunitonanaxiswillsimplyrepeatour
firstunit.Thatistosaythatthecrystalisexactlythesamefrom0to1asitisfrom1to2
unitsoftheunitcell.Therefore,weonlyhavetoconcernourselveswithfacesandplanes
within1unitvalueofeachaxis.
Forthephyllosilicateminerals,3facesareofconcernforus:the(100),(010),and
(001).These3planesarerepresentedschematicallybelow.Lookingbackacoupleof
pagesyoucanseetheusualorientationofthephyllosilicates.Inthisorientationthe(100)
and (010) faces will have similar properties; the (001) plane, however, will be very
different. The(001)planeiscomposedofsurfaceoxygengroupsthatarecompletely
charge(andcoordinatively)satisfied,makingthemchemicallyunreactive. Incontract,
thesurfacegroups,eitheroxygensorhydroxyls,onthe(100)and(010)facesarenot
chargebalancedorcoordinativelysatisfied.Theywillthereforebechemicallyreactive
andgenerateachargesimplyfromtheirunsatisfiedcoordinationenvironment(terminal
bonds).

13
z

1 (0 0 1 )
(100)
y

1
1
x

(0 1 0 )

I7,Phyllosilicates
Asalreadystated,thephyllosilicatesaremineralscomposedofSi,Altetrahedral
andMgorAloctahedra.Thephyllosilicatesareclassifiedbasedupon:
1.Thenumberoftetrahedraandoctahedrainalayer
2.Theoctahedralsiteoccupancy(i.e.,octahedralcomposition)
3.Thechargeperformulaunitforeachlayer.
Thedominantmineralswewillstudyareprovidedinthefollowingtable,basedonthe
specifiedcriteriaabove.
GeneralClasses(layerbuildup)ofPhyllosilicateMinerals:
LayerType

Charge

Trioctahedral

Dioctahedral

1octahedra

brucite,Mg(OH)2

gibbsite,Al(OH)3

1tet.:1oct.

serpentine,Mg3Si2O5(OH)4

kaolinite,Al2Si2O5(OH)4

2tet.:1oct.

talc,Mg3Si4O10(OH)2

pyrophyllite,Al2Si4O10(OH)2

2tet:1oct.

phlogopite
KMg3(AlSi3O10)(OH)2

muscovite
KAl2(AlSi3O10)(OH)2

biotite
KFe3(AlSi3O10)(OH)2

0.60.8

illite(hydrousmica)
K(Na,Ca)Al1.3Fe0.4Mn0.2Si3.4Al0.6O10(OH)2

0.60.9

vermiculite

14

0.250.6
Thelayerchargeperformulaunit

smectite

I8,MineralDescriptions
NonexpandableClayMinerals
Brucite andGibbsite: Gibbsiteisacommonsecondarymineral,anditisasinkfor
aqueousAl.Bruciteislesscommonlyobservedinsoilsbutisfoundinthosederived
fromultramaficparentmaterials.
SerpentineandKaolinite:Thestructuralsheetscomposedof1tet.to1oct.areheld
together byHbonds. Becauseofthenumerous bondsthesesheets areheldrather
tightlytogetherandarethusonlyslightlyexpandable.
Serpentine, like brucite, is found most commonly in soils derived from ultramafic
material;itexhibitsatubularmorphologyduetodifferencesbetweentheoctahedral
andtetrahedrallayers.(Incidently,asbestosiscomposedofserpentinemineralsandis
hazardoustolungtissuebecauseofitsfiberoushabitaconsequenceofthetubular
morphology).
Kaoliniteisacommonsoilmineralandmaybethemostubiquitousofallsoilminerals.
Ithasalowcationexchangecapacityvalue(vidainfra)rangingfrom10to100mmol/
kg;thechargeoriginatesfromunsatisfiedbondsattheterminalendsofthesheetsandis
pHdependent.Thesurfaceareaisalsolow,typicallybetween7and30m2/g.
TalcandPyrophyllite:Thesemineralsarethestructuralbasisforthe2:1clayminerals.
They,however,havenopermanentcharge. Adjoininglayersarebondedviavander
Waalsforces.Asaconsequence,themineralisveryeasilycleavedalongthisbonding
planeandaccountsfortheslipperinessoftheseminerals;theyhaveminimalCEC.
Micas (phlogopite,muscovite,andbiotite):1Alsubstitutes forevery4th Siinthe
tetrahedral sheetofthemicas. This producesachargeof1performula unit; the
additionalchargeissatisfiedbyK+ ionsthatresidesintheinterlayercavities andis
bound such that it is not exchangeable. The high layer charge results in a strong
assemblageofthelayerswhicharethusnonexpandable;thereisnoappreciableCEC.
Potassiumdoeshavearoleinthiscollapse;itistheperfectsizetofitinthecavities
betweenlayersandallowsforthecollapseoftheselayers.
Thetrioctahedralmicasweathermorerapidlythanthedioctahedralones.TheK +inthe
interlayerisreleasedduringweatheringasourceofnutrientsinsoils.

15
ExpandableClayMinerals
The layer charge of these minerals is reduced relative to mica. This occurs from a
numberofprocessesincluding:
i)Fe(II)oxidationtoFe(III)
ii)H+incorporationintothestructure
iii)exchangeofSi4+forAl3+inthetetrahedralsheet
iv)cation(e.g.,Al3+forMg2+)substitutionsintheoctahedrallayer
Illite(hydrousmica):Thismineralisderivedfromtheweatheringofthemuscovite.It
differsinthatadivalentcationsubstitutesintheoctahedrallayerforAl. Also,the
quantityofSiisincreasedinthetetrahedrallayer. TheCECisapproximately300
mmol/Kg(30meq/100g).
Vermiculite:Canoccurineitherdiortrioctahedralforms.Approximateformulasfor
theseare:
dioctahedral:Nax(Al,Fe)2(AlxSi4x)O10(OH)24H2O
trioctahedral:Nax(Mg,Fe)2(AlxSi4x)O10(OH)24H2O
Thechargeoriginatesprimarilyfromisomorphicsubstitutioninthetetrahedrallayer
(Al for Si). The charge in the tetrahedral layer may be somewhat offset by Al 3+
substitution for Mg2+ in the octahedral layera source of positive charge that
diminishes (slightly) the negative charge developed in the tetrahedral sheet. The
cationsintheinterlayer,whichbalancethelayercharge,areexchangeable.Duetoa
relativelyhighlayerchargethatoriginatesfromthetetrahedrallayer,thelayersarenot
veryexpandable. Ionsofthecorrectsizetofittheinterlayercavity canleadtoa
layercollapseofthestructure;suchionsincludeK+,NH4+,Cs+,Rb+.Oncetheseions
collapsethestructuretheyarenolongerexchangeable.TheCECandsurfacearea(SA)
arehigh,generallyontheorderofCEC=12001500mmol/Kg,SA=600800m 2/g.
Smectites: Thesmectite minerals arethemostexpandable oftheclay minerals and
accountformostoftheobservedshrinkswellpropertiesinsoils.Thisisduetotheir
moderatelylow layer charge. Additionally, they have a very high water holding
capacityasaresultofsuchswelling.Likethevermiculiteminerals,smectitescanbe
foundinbothdioctahedralandtrioctahedralforms.
DioctahedralForms:
Montmorillonite:Nax(Al2xMgx)Si4O10(OH)2

Mg2+issubstituted
forAl3+intheoctahedrallayer
x=0.250.45

16

Beidellite:Nax(Al2)AlxSi4xO10(OH)2
TrioctahedralForms:
Saponite:Naxy(Mg3yAly)AlxSi4xO10(OH)2

Al3+substitutedforSi4+in
tetrahedrallayer
x=0.450.5
Al3+substitutedforSi4+in
tetrahedrallayerandforMg2+in
octahedrallayer

Hectorite:Nax(Mg3xLiy)Si4O10(OH)2
TheCECrangesfrom800to1200mmol/Kgwithasurfaceareaof600800m 2/g.
Thesemineralshaveverysmallparticlesizesandarehighlyexpandable.Theyarethe
major components of soils that limit water movement in dispersed soils.
Montmorilloniteiscommerciallyavailableunderthename"Bentonite",whichisused
asannonpermeablematerialforpondsorearthendamns.
Integrades: Thereisapotentialforcationic metals suchasAl 3+,Cr3+,andFe3+ to
precipitatewithintheinterlayersofthe2:1mineralsthathaveapermanentcharge;these
precipitatesmaybegenerallytermed'hydroxyinterlayers'.Interlayerprecipitatesarein
essence an additional octahedral layer, forming a 2:1:1 type mineral, if complete
interlayeroccupancyisachieved.Usually,fulloccupancyoftheinterlayerisnotreached
andsotheresultingphaseistermeda2:1integrate.IntegradesdecreasetheCECofthe
mineral but often increase the anion exchange capacity (AEC). The interlayer
precipitates also decrease the phyllosilicate's surface area, expandability, and water
holdingcapacity.Theyoccurmostcommonlyinvermiculitebutarealsofoundinsome
ofthesmectiteminerals.
Chlorite:Truechloriteisaprimarymineralwitha2:1:1layerstructure(alsocalled2:2)
andhastheformula(AlMg2(OH)6)x{Mg3(Si4xAlx)O10(OH2)}.Notethatchloriteisa
trioctahedral mineral (both octahedra have Mg as the primary cation) with some Al
substitutingintheadditionaloctahedralsheet.Thesurfaceareis70to150m 2/gandthe
CEC 100400 mmol/Kg. Again some positive charge is associated with the Al
substituted octahedral layer giving rise to anion exchange. Pedogenic chlorites are
actuallyendmembersoftheintergradesdiscussedabove.
Tectosilicates(Frameworksilicates)

Extending the layer silicates to a three dimensional structure, so that every

tetrahedra shares allofits4oxygenswithneighbors,resultsintheclassofminerals
knownasthetectosilicates.Themostcommonandwellknownmemberofthisgroupis

17
quartz(SiO2).Asshouldbeexpectedbyitsabundanceinthesurfaceenvironment,the
structuralarrangementofthetectosilicatesleadstoaverystableconfigurationthatresists
weathering. Another well known member of this group are the Feldspars. While
abundantissomesoils,thetectosilicatesdonotsignificantlycontributetothechemicalor
electrostaticpropertiesofsoils;theyarerelativelyinertduetotheirstableconfiguration.
Zeolites are also tectosilicates; they are unique minerals having a 3D
aluminosilicate framework that forms channels and cavities of distinct size. These
channelscanactlikemolecularsievesandaccountfortheuseofzeolitesascatalystsof
petroleumproducts. Thealuminosilicatetetrahedraareconnectedbytheirverticesand
arecomposedof4to12memberringslinkedtogether;inthecenteroftheringsarethe
channels.
AccessoryMinerals:TheHydrousOxides
Inwelldeveloped,highlyweatheredsoilsthephyllosilicateclayfractionbeginsto
diminishgivingwaytoAlandFeoxides,hydroxides,andoxyhydroxides(collectively
referredtoashydrousoxides). Becausethesematerialsformlateintheweathering
sequenceandattheexpenseofotherminerals, theyarealsoreferredtoassecondary
minerals.Duetotheirhighsurfaceareas,abilitytocoatotherparticles,andreactivity,
hydrousoxidescanexhibitamarkedinfluenceonthesoilchemicalpropertiesevenwhen
composingonlyasmallfractionofthetotalsolids.Mostofthesecondarymineralsdo
nothavepermanentcharges,buttheydohaveaveryactivevariablecharge.Becauseof
theirstructure,allsurfaceplanes willbecoordinatively unsaturatedandconsequently
develop a variable charge. In addition, this results in the surfaces having a strong
CHEMICALaffinityformanyions,whichleadstoaverystrongretentionofionson
suchsurfaces.
Silica:Inadditiontotheverystabletectosilicateforms,hydratedamorphousformswith
very high surface areas are also common in soils. These materials are not rigid
structures,rathertheyformagellikeamorphousphases. Theycancontributetothe
cementation of clay rich layers. The ZPC is low (at pH 23) so that the dominant
electrostaticinteractionwillarisewithcations.
Allophane:AgenerictermforamorphoushydratedaluminosilicatewithaSi:Alratioof
12. Aluminum enters octahedral coordination and Si is present in tetrahedral
coordination.Theyarecommonlyobservedinvolcanicallyderivedsoilsandsediments.
Theexchangecapacityofallophanesisverylarge;valuesofupto1500mmol/Kghave
beenreported. Asmightbeexpected,theirsurfaceareaisalsolarge(70300m 2/g).
Allophane forms a spheroid surface topography and has short to midrange atomic
ordering.
Imogolite: (SiO2Al2O32.5H2O) Similar to allophane, imogolite is also a common
material found in soils derived from volcanic parent material. It has a tubular
morphology,incontrasttothesphericalmorphologyofallophane.Italsohasaveryhigh
CEC(1350mmol/Kg).

18
Hydrous Al Oxides: The most abundant of the secondary minerals is gibbsite,
Al(OH)3. Itisaverystablemineralatlowtemperaturesandisthebuildingblockfor
otherphyllosilicates(thedioctahedralclass).Ingibbsite,hexagonalsheetsareboundby
Hbonds.It,liketheotherhydrousAloxides,hasaveryhighZPCthatrangesfrom8to
9.5.Thesurfaceareaofthismineralismoderate,520m 2/g.Itisfoundubiquitousin
welldevelopedsoils,particularlyofthetropic. AnotherAlphasefoundinsoilsand
sediments is boehmite (AlOOH). It is the analog to lepidochrosite, an iron
oxyhydroxides.
HydrousFeOxides:Ferrichydrousoxidesareabundantinmanysoilsandduetotheir
strongpigmentationtheyareeasilyrecognized;theyellowandredsoilcolorsaredueto
this class of minerals. Based on radius ratios, Fe(III) should enter octahedral
coordination,andthisisobservedinnature.Accordingly,theFeoxidesaresimilartothe
Aloxides.
Goethite(FeOOH)isthemostabundantoftheHFOsbutiscloselyfollowedby
hematite (Fe2O3). Goethite exhibits a yellowish color and is common in lower
temperature,highermoisturesoils.Hematiteformsabrightpinkishcolor,andisfavored
inhightemperaturelowmoistureareas.Additionally,highpHfavorstheformationof
hematite relative to goethite. The surface are of goethite is slightly higher than for
hematite(1050m2/gforgoethiteand520m2/gforhematite).Ferrihydriteisanother
commonformofFeissoil,andalthoughnotasstableaseitherhematiteorgoethiteit
formsrapidlyfromFe(III)precipitation.Givenenoughtimeferrihydritewilltransform
toeithergoethiteorhematite.Ironoxideshaveastrongaffinityformanymetalionsand
consequentlyareusedinwastewatertreatmentstopartitionmetalsoutoftheaqueous
phase.Theyalsoformconcretionsandcoatingsinmanysoils.
ManganeseOxides:Themanganeseoxidesareanimportantfractionofthesoilbecause
theyareoneofthestrongestoxidantsofnaturallyoccurringmaterial.Theyalsohavea
veryhighaffinityforcationicmetalssuchasFe(III),Al,Zn,Cu,etc.Inmarinesystems,
nodules composed of concentric rings alternating between Fe and Mnoxides are
common.Theseinterestingnoodlesresultfromredoxtransformationandtendtoberich
inothermetalssuchasCoaswell.
ThemostprevalentMnoxideinsoilsisthemineralbirnessite(adisordered
MnO2phase).Manganeseoxidesformcoatingsonmanyparticlesbutarealsoobserved
as discrete nodules; their strong black pigment often dominates the soil color
occasionallythisismisidentifiedasarisingfromorganicmatter.Thesematerialsusually
havealowZPC,highsurfacearea,andareveryreactive.Theyarealsooneofthefirst
materialslosttoreductivedissolutionunderoxygenlimitingconditions.
TitaniumDioxides: Aresidualfromtheprimaryminerals,thetitaniumdioxidesare
foundin lesser amounts in soils. They do have both ananion andcation exchange
capacityduetoamoderateZPCnear56.Therearetwopolymorphs(mineralswiththe

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samechemicalcompositionbutdifferingstructures)ofTiO2,rutileandanatase.Bothare
foundinsoils,butrutilealittlemorecommonly.Bothofthesemineralsarestrongwhite
pigments and account for the white color of paints. In fact, anatase and rutile are
extensivelyminedaspigmentsforpaints.