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Soil organic matter

Chapter · January 2000

DOI: 10.1038/194324b0

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 In Sumner,M.E. (Editor-in-chiefl
2000.
Handbookof Soil Science.
CRCPress,BocaRatonUSA.p 825 - 884

SoilOrganicMatter
|.A. Baldock
Division of kmd and.Water, CSIRO,CIen Osmond.Ausualia

P.N. Nelson
Division of Land and Water, CSIRO, Tovvnsville, Australia

2.1 Introduction and Definitions

Researchpertainingto theorganicfractionof soilscanbe tracedbackmore than200 yr. Achard ( 1786)
isolateda dark amorphousprecipitateupon acidificationof an alkalineextractfrom peat.The effect
of organic matter on soil N fertility (Liebig, 1840),and studieson the use of animal manuresfor
maintainingsoil fertility (Lawes, l86l) and the influenceof soil and tree specieson the development
of humus form (Muller, 1887)demonstratedthe importanceof organicmatterin soil processes. The
advancementof organic chemical methodologiesand confirmation of the presenceof various
chemical structuresin soil organic matter (SOM) lead to theoriesthat SOM was composedof a
heterogeneousmixture of dominantly colloidal organic substancescontaining acidic functional
groups and N. More recently, the polyphenol theory was proposedin which quinone structuresof
lignin andmicrobial origin polymerizein thepresenceof N containinggroups(amino acids,peptides,
and proteins)to producenitrogenouspolymers (Flaig et al., 1975).The early researchpertainingto
SOM has been reviewedby Stevenson(1994). While alkaline extractionof SOM is still practiced,
modernanalyticaltechniques,includingsolid-statetrCnuclearmagneticresonancespectroscopy('rC
NMR), infrared spectroscopy(IR), and pyrolysis gas chromatography/massspectroscopy(Py-
GCMS) allow selectiveprobingof the chemistryof SOM within samplesof whole soil, and avoid the
problems of incomplete extraction, lack of biological significance,and artifact synthesisoften
ascribed to alkaline extraction procedures.The combination of these techniques with novel
approaches capableofidentifying biologicallyimportantfractionsofSOM hassignificantlyadvanced
our knowledgeof the organicfractionof soils and its dynamicsover the last 20 years.
Despitesucha long history of researchand new methodologicaland technologicaladvancements,
many questionsrelatedto the genesisandchemicalcompositionof organicmaterialsin soilsand their
impactson soil fertility, pedogenesis,and soil physicaland chemicalpropertiespersisttoday.Many
excellenttexts and review papershavebeenwritten on the topic of SOM; someof the more recentof
thesearegiven in Table2.l.
An examinationof termsusedto describeSOM and its componentsin the literaturerevealeda lack
of precisedefinitionsof what SOM and its variousfractionsrepresent.Sucha problemexistsbecause

B-25
B-26 SoilChemisrry

Table 2.1 List of textsand reviewarticlespenainingto the studyof soil organicmatterreleasedsince1985.Indi-

vidual review articleswithin texts havenot beenidentified separatelyfmodified from Hedgesand Oades,I997j

Texts
Humic sutrstancesin soil, sedimentandwater(Aiken et al., 1985)
Soil organicmatterandbiologicalactivity(VaughanandMalcolm, 1985)
Interactionsof soil mineralswith naturalorganicsandmicrobes(HuangandSchnitzer,1986)
Cyclesin soil: carbon,nitrogen,phosphorus, (stevenson,1986)
sulfur,micronutrients
Chemistryof soil organicmatter(Kumada,1987)
Soil organicmatter(Tate,1987)
Humic substances andtheir role in the environmenl(FrimmelandChristman.1988)
Dynamicsof soil organicmatterin tropicalecosyslems (Colemanet al., i989)
Humic substances II: In searchof structure(Hayeset al.. 1989)
Soil microbiologyand biochemistry(PaulandClark, 1989)
Soil Biology and Biochemistry,Vol. 6 (BollagandStotzky,1990)
Humic substances in soil andcrop science(MacCarthyet al., 1990a)
Advancesin soil organicmatterresearch: The impacton agricultureandtheenvironment(Wilson, 199I )
Soil Biology andBiochemistry,Vol. 7 - Vol. 9 (StotzkyandBollag, 1992,1993,1996)
Soil organicmatterdynamicsandsustainability of tropicalagriculture(Mulongoyand Merckx, 1993)
Environmental organicchemistry(Schwartzenbach et al., 1993)
Humic substances in the globalenvironment(Senesiand Miano, 1994)
Humuschemistry:genesis,composition,reactions(Stevenson, 1994)
Soil organicmattermanagement for sustainableagriculture(Lefroyet al., 1995)
Humic substances of soils andgeneraltheoryof humification(Orlov, 1995)
Carbonforms and functions in forest soils (McFee and Kelly, 1995)
The role of nonlivingorganicmatterin theearth'scarboncycle(7rpp andSonntag,1995)
Drivenby nature:plant litter qualityanddecomposition (CadischandGiller, 1997)
Soil organicmatterin temperate ecosystems (Paulet al.. I 997)

ReviewArticles
The retentionof organicmatterin soils(Oades,1988)
An introductionto organicmatterin mineralsoils(Oades,1989)
Soil organicmatter- the n€xt75 years(Schnitzer,l99l)
Physicalfractionationof soil organicmatter in primary particle size and densityseparates(Christensen,1992)
A hierarchicalmodel for decompositionin terrestrialecosystems- applicationto soils of the humid tropics (Lavelle
et a1..1993)
Organic matterin tropical soils - currentconditions,concernsand prospectsfor conservation(Ross, 1993)
Modelling food webs and nutrient cycling in agro-ecosystems (Deruiter et al., 1994)
Towards a minimum data set to assesssoil organicmatterquality in agriculturalsoils (Gregorichet al., 1994)
The chemicalcompositionof soil organicmatterin classicalhumic compoundfractionsandin bulk samples- a review
(Beyer,1996)
Carbon in primary and secondaryorgano-mineralcomplexes(Christensen.1996)
Applications of NMR to soil organic matteranalysis- history and prospects(Preston,1996)
Characterization of humic andsoil particlesby analyticalpyrolysisand computermodeling(Schultenand Leinweber,
r996)
Life after death- lignin-humic relationshipsreexamined(Shevchenkoand Bailey, 1996)
Stabilizationand destabilizationof soil organicmatter- mecbanismsand controls(Sollins et al., 1996)
Soil Orpanic Matter B-27

of the heterogeneityof organic material found in soil in terms of its source,chemical and physical
composition, diversity of function, and dynamic, ever changing character.The term SOM has been
usedto encompassall organicmaterialsfound in soil (Stevenson,1994),excludingcharcoal(Oades,
1988),or excluding nondecayedplant and animal tissues,their partial decompositionproducts,and
theliving soil biomass(MacCarthyet a1.,1990b).As suggestedby MacCarthyet al. ( I 990b),it is most
important that readersestablishhow particular authorsapply the various terms to fully understandand
assessthe implicationsof commentsmade.However, it is also importantthat a set of definitionsfor
SOM and its componentsis derived and applied consistently.The definitions of SOM and its
romponentsto be utilized in this chapter(Table2.2)have beenderivedfrom severalsources(Oades,

Table2.2 Definitionsof soilorsanicmatterandits comoonents

Component Definition
Soil organicmatter(SOM) The sumof all naturalandthermallyalteredbiologicallyderivedorganicmaterialfound
of its source,whetherit is living or dead,
in the soil or on the soil surfaceirrespective
or stageof decomposition, but excludingthe aboveground portionof Iiving plants.
LrvingComponents of plantorigin.Standingplantcomponents
Living tissues whicharedead(e.g.,standing
Phytomass deadtrees)arealsoconsidered asphytomass.
\{rcrobial Biomass Organicmatterassociated with cellsof living soil microorganisms.
FaunalBiomass Organic matterassociatedwith living soil fauna.
NonlivingComponents Organic tiagmentswith a recognizablecellular structurederivedfrom any sourcebut
Particulateorganicmatter usually dominatedby plant derivedmaterials.
Litter Organic materialsdevoidof mineralresidueslocatedon the soil surface.
Macroorganicmatter Fragmentsof organicmatter> 20 pm or > 50 pn {i.e., greaterthan the lower size limtt
containedwithin the rnineralsoil matrix and typicallyisolatedby
of the sandfraction)
sievinga dispersedsoil.
Light Fraction Organicmaterialsisolatedfrom mineralsoilsby flotationof dispersedsoil suspensions
on wateror heavyhquidsof densitics1.5- 2.0 Mg m r.
Dissolvedorganicmatter Water solubleorganiccompoundsfoundin the soil solutionwhich are < 0.45 pm by
definition.Typically this factionconsistsof simplecompoundsof biologicalorigin
(e.g.,metabolitesofmicrobialandplantprocesses) includingsugars,aminoacids,low
molecularweightorganicacids(e.g..citrate,malate,etc,)but may alsoincludelarge
molecules.
Humus Organic materialsremainingin the soil after removalof macroorganicmatter and
dissolvedorganicmatter.
Non-humic Identifiable organic structureswhich can be placed into discrete categoriesof
biomolecules biopolymersincludingpolysaccharides and sugars,proteinsand amino acids.tats,
waxesandotherlipids,andlignin.
Humicsubstances Organicmoleculeswith chemicalstruclureswhich do not allow them lo be placedinto
the categoryof non-humicbiomolecuies.
Humic acid Organicmaterialswhicharesolublein alkalinesolutionbut precipitateon acidification
of the alkalineextracts.
Fulvic acid Organic materialswhich are soluble in alkaline solution and remain soluble on
acidificationof the alkalineextracts.
Humin Organicmaterialswhich areinsolublcin alkalinesolution-
Ineft organicmatter Highly carbonizedorganic materialsincluding charcoal,charred plant materials,
graphiteand coal with long turnovertimes.
B-28 Soil Chemistry

1988;MacCarthy et al., 1990b;Stevenson,1994)and are put forward in an effort to reduceexistins

variationsin the useof the terms.

2.2 Functions of Soil Organic Matter

The organic fraction of soils often accountsfor a small but variable proportion of total soii mass.
O r g a n i c C c o n c e n t r a t i o n s r a n g i n g f r o m < 5 g C ksgo- il l f o r d e s e r r l o a m s ( A r i d i s o l s ) t o > 1 3 0 g C k g - '
soil for alpinehumussoils (Histosolsand Mollisols) werepresentedfor the0-i 0 cm layer of the great
soil groupsof Australia(Spainet al., 1983).Sombroeket al, (1993)presentedtopsoil and subsoil
organicC contentvaluesrangingfrom 0.5-3 g C kg-'for Yermosolsup to 310-555 g C kg-rfor
Histosolsusing 400 soil profiles groupedaccordingto FAO soil units.Contentsof organicC on the
order of 441-549 gC kg -i and 440-550 g C kg-t were measuredfor Canadianpeats(Prestonet a1.,
1989b)and Germanforest litter layers(Zech et al., 1992),respecrively.
Despiteits oftenminor contributionto the total massof mineralsoils,the organicfractioncanexert
a profound influence on soil properties,ecosystemfunctioning, and the magnitude of various
obligatoryecosystemprocesses(Table2.3).The soil propertieswhich organicmatterinfluenceshave
beenclassifiedinto three broad groups:biological, chemical,and physical properties.It should be
noted that strong interactionsand interdependencies exist betweenthesegroups.For example,the
ability of organicmatterto chelatemuitivalentcationscanaffectits potentialto stabilizesoil structure
and alsoits biodegradability(JusteandDelas, 1970;Justeet al., 19?5;Gaiffe et a1.,i 984; Muneer and
Oades, 1989a,b,c).In addition, the effects of organic matter on soil properties often involve
interactionswith the soil mineralfraction,and variationsin soil propertiesnotedacrossdifferent soils
may not be solelya consequence of qualitativeor quantitativevariationsin the soil organiccomponent.

2.2,1 BiochemicalFunctions

2.2.1.1 Reservoir of Metabolic Energy

The most fundamentalfunction of the organicfraction of soils is the provision of metabolicenergy
which drives soil biological processesand the direct and indirecteffectswhich this has on other soil
propertiesand processes.Photosynthesis fixes CO, into glucosewhrch is then convertedinto a wide
rangeof organiccompounds(e.g.,cellulose,hemicellulose,lignin, lipids, proteins,etc.) by various
enzymaticprocesses.The C fixed into such compoundsis depositedin or on the soil during plant
growth and as the plant or a portion of its tissuessenesce,therebyproviding C substratesfor soil
macro- and microdecomposerorganisms.As the organicC is utilized by decomposerorganisms,it is
eitherassimilatedinto body tissues,releasedasmetabolicproducts,or respiredas CO". Oades(1989)
presentedan estimate of the C flow through a fertile grasslandwhere primary production via
photosynthesiswas l0 Mg C ha-r yr-'. Of the 3 Mg C ha-r yrr that was addedto the soil organicC
fraction, the soil fauna were estimatedto utilize 0.3--0.45Mg C hrryr-r, while the soil microbial
biomasswas estimatedto utilize 2.4Mg C ha-ryr-'. The majority of organic matter processingis
thought to be completedby the soil microbial biomass.However, other activities of the soil fauna
enhancethe ability of soil microbial decomposersto utilize organic residuesadded to soil. These
include ( I ) fragmentationof plant debris, which enhancesthe surfaceareaper unit weight of piant
residueavailableto microbial attack,and(2) distributingorganicmaterialsthroughoutthe soil matrrx,
which provides an avenuefor greatercontact between decomposermicroorganisms and substrates.

2.2.1.2 Source of Macronutrients

A resultof the utilization of organicmaterialsby soil organismsis a conversionof macronutrients(N,
P, and S) within organicchemicalstructuresinto inorganicforms, which are either immobilized and
Soil Organic Matter B-29

Table 2.3 Propertiesand functionsof organicmatter in soil

Property Function
BiolosicalProperties
Reservoirof metabolicenergy Organic matterprovidesthe metabolicenergywhich drives soil
biologicalprocesses.
Sourceof macronutrients The mineralizationof soil organicmattercan significantly
influence(positivelyor negatively)the sizeof the plant available
macronutrient (N, P, andS) pools.
Ecosystemresilience The build up of significant pools of organicmatter and associated
nutrientscan enhancethe ability of an ecosystemto recoverafter
imposednaturalor anthropogenic perturbations.
Stimulation and inhibition of enzyme The activityof enzymesfoundin soilsandthe gowtb of plants
activitiesandpiant andmicrobialgrowth andmicroorganisms can be stimulatedor inhibite.dby the presence
of soil humicmaterials.
PhysicalProperties
Stabilizationol soil structure Throughthe formationof bondswith the reactivesurfacesof soil
mineralparticles,organicmatteris capableof bindingindividual
particlesand aggregations of soil particlesinto water-stable
aggregates at scalesrangingfrom < 2pm for organicmolecules
throughto mm for plant roots and fungal hyphae.
Waterretention Organic mattercan directly affect water relention becauseof its
ability to absorbup to 20 timesits massof waterand indirectly
throughits impacton soil structureandporegeometry.
Low solubility Ensuresthat the bulk of theorganicmaterialsaddedto the soil are
retainedand not leachedout of the soil profile
Color The dark color which soil organicmatterimpartson a soil may
altersoil thermalproperties.
ChemicalPropertief
Cationexchangecapacity The high chargecharacteristicsof soil organicmatter enhance
retentionof cations(e.g.,Alrt, Fe3*,ca2*,Mg2*,NH4*,and
transitionmetalmicronutrients).
BufferingcapacityandpH etfects In slightlyacidicto alkalinesoils,organicmattercan act as a
buffer andaidsin the maintenance of acceptablesoil pH
conditions.
Chelationof metals Stablecomplexesformedwith metalsandtraceelementsenhance
the dissolutionof soil minerals,reducelossesof soil
micronutrients, reducethe potentialtoxicity of metals,and
enhancethe availabilityof phosphorus.
l n t e r a c t i o n sw i t h x e n o b i o t i c s Organicmattercan alterthe biodegradability, activityand
sistenceof oesticidesin soils.

usedin the synthesisof new tissueswithin soil organismsor mineralizedand releasedinto the soil
mineralnutrientpool- With the exceptionof intensivelymanagedsoil receivingsignificant inputsof
macronutrientsin the form of fertilizers,organicmatterprovidesthe largestpool of macronutrientsin
the soil. McGill and Cole (1981) proposedthat the mineralizationof C, N, P, and S followed a
dichotomous system involving both biological and biochemical mineralization. Biological
mineralizationis driven by the needofdecomposerorganismsfor C as an energysourceand accounts
for the mineralization of N and C bonded S. Biochemical mineralizationrefers to the releaseof
phosphateand sulfate from the P and S ester pool via enzymatic hydrolysis outside of the cell
B-30 Soil Chemistrr

membrane.As a result and in contrastto organicN, organicP and S accumulationand mineralizatic'n

in soilscan occur independentlyof C and N dynamics.This leadsto the potentialfor large variations
in C:N:P:Sratios in SOM. An avcrageC/N/PISratio of fi'l:7.7:1: i was presentedby Stevenson
( 1986)for SOM. In the next severalparagraphs,the contentsand chemicalstructuresof soil organiz
N, P, and S and ratios of organicC/N, C/P, and CIS will be discussedto provide an indicationof the
organicforms and potentialstoresof macronutrientswithin SOM. More detailedpresentations of the
forms and availability of organicN, P and S, can be lbund in SectionC, Chapters3 and 4.

Nitrogen
The soil N pool is dominatedby N fbund in organicstructures.in soilswith significantcontentsof Ki-
containingclay minerals(e.g.,illite) capableof fixing NHo*,approximateiy9OVoof the soil N is
containedin organicstructures,870existsasfixed NHo',and l-3Vo canbe found in the inorganicplant
availablepool (NO]- andNHo').In soilswith little capacityto fix NHo*in clay minerals,the proportion
of organicN is > 977oand the inorganicfractionis l-37o. On a global scale,Sbderlundand Svensson
( 19?6)esrimarcdthat the organicN fractionof soilsaccountedfor 959aof the total soil N pool, which
is equivalentto the averagevaluepresentedby Bremner(1967).The C/]'{ratio of SOM dependson the
CA{ ratio of the vegetationalinputsand the degreeto which they aredecomposed.Organicmateriais
that have cycled through the dccomposerbiomassgenerallyhave CAI ratios of 12-16, whereas
undeconposed fragmentsof plantlitter andorganicmaterialsin peatdeposits,wheredecompositit'n
is hinderedby anaerobicconditions,can havemuch higherCA{ ratios'
Soil organicN hasbeentraditionallydivided into the foliowing five fiactions basedon a varietyof
acidhydrolysisprocedures:( 1) acidinsolubleN, (2) ammoniaN recoveredafterhydrolysis,(3) amino
acid N, (4) amino sugar N, and (5) hydrolyzableunidentifiedN. Data summarizedby Stevenson
( 1994)for 1 I stuclieswhereacidhydrolysisprocedureswereappliedto diffcrent soil typesshowedthat
therewas asmuch variationin the contentsof eachform of N within similar soils asbetwcendifferent
soil types.The proportionsof eachform of organicN were744c/o acid insolubleN'9-37Vo ammonia
N, t:-SOZ, amino acid N ,l-l4flo amino sugarN , and 440% hydrolyzableunidentifiedN' Although
methodologicaldifferencesmay accountfor a portionof the largevarialionsnotedin the compositron
by acrd
of soil organicN, it is evidentthat approximately50Vaof the total soil N cannotbe identified
hydrolysisprocedures(acid insoluble N + hydrolyzable unidentified N).
gel
Inirial uit"-pt, to identify the chemical compositionof unidentifiable organic N utilized
and gas chromatography/mass spectroscopy (GCnvlS) (Schnitzer
filtration followed by acetylation
point pyrolysis-GC
1985;Schnitzerand spiteller,1986).Schultenet al, (199-5,1997)utilizedcuric
of the pyrolysis products.These studies suggested that heterocyclicN
MS with N selectivedetection
1997
compoundsrepresentedanimportantcomponentofunidentifiedsoilorganicN(Schultenetal"
chemical structure of the heterocyclic N compounds)' The formation ot
presentedexamplesof the
-heterocyclic r5NH3 by humic substances (IHSS Suwannce
N compoundsvia nonbiologicalfixation of
and by reacting riN labeledanalinewith humri
River fulvic acid and peatand leonardite humic acids)
(1996),respectively.In contrast
materialswas noredby Thorn and Makita (1992)and by Thorn et al.
solid-state riN nuclearmagnetictesonance(NMR) spectroscop)
to theseresults,studiesutilizing
spectratendto be dominated
havefailed to observesubstantialcontributionsfrom heterocyclicN, and
and terminal amino groups(Knicker and Ludemann' 1995;Knicker et
by signalsarisingfrom amides
addresstheseinconsistencies'and to
al., 1995; Clinton et al., 1995).Further effort is required to
which cannot be identified by
quantitativelycharacterizethe composition of the fraction of N'
conventionalacid hydrolysisprocedures'
Soil Organic Matter B-31

Phosphorus
The compositionand cycling ofsoil organic P have beenrecently reviewed by Stevenson(1986,
1994),and SanyalandDeDatta( 1991).As a resultof potentialadsorptionand inorganicprecipitation
reactionscapableof reducingthe availabilityof P in soils,mineralizationof r:rganicP is impor"tantto
soil fertility (Tiessenet al,, 1984;Beck and Sanchez,1994).The relative imporranceof organicp as
a nutrientsourcetendsto be greateron highly weatheredsoils (Duxbury et al., 1989).The principal
organic P'containing compounds in soils and their approximate proportions include inositol
phosphates(2*5AVa),phospholipids(1*57o),nucleic acids (0.2-2.5Vo),Lraceamountsof phospho-
proteins, and metabolic phosphates(Stevenson,1994). Soil organic P accounts for a variable
proportion of the total soil P. Halstead and McKercher (1975) and Uriyo and Kessaba(1975)
presentedsoil organicP valuesrangingfrom 4-1400 pg g-' soil which accountedfor 3-90Vo ofthe
total soil P. Uriyo and Kessaba( I 975)derivedtherelationshipbetwe€norganicP and organicC given
in Equation[2. 1] which producesan organicCIP ratio of I 15 andis consistentwith the averagevalue
of 1 l7 proposedby Stevenson(1994). However,large variationsin the organic C/P ratio (61-526)
havebeennotedfor Finnish soils (Kiala, 1963).

OrganicC (mg g-' soil) = 4.9 + 0.059 OrganicP (pg g-' soil) (R?= 0.49) t2.11
Salfur
Reviewsof the cycling and chemicalcompositionof soil organicS includeStevenson(1986, 1994),
Germidaet al. (1992), and Nguyen and Goh (1994).Sulfur-containingorganiccompoundsfound in
soils are generallygrouped into two pools: compoundsin which the S can be reducedto HrS by
hydroiodicacid (HI), andcompoundsin which the S is directly boundto C. The HI reduciblefraction
consistsmainly of estersulfates(C-O-S bonds)and someestersulfamates(C-N-S bonds).The C
bondedS fractioncontainsaminoacid S (C-S bonds)or sulfonates(C*SO,""bonds). The estersulfates
andsulfamatesaretypically associatedwith aliphaticsidechainsof soil organiccompounds(Bettany
et al., 19?9),while the C bondedS is incorporatedalong with C and N into the core of soil organic
compoundsand is generallylessbiologicaliy accessible(McGill and Cole, 198l; Stervartand Cole,
1989).OrganicS typically accountsfar > 9AVoof the total S found in non-salineand non-tidal soils
(Nguyenand Ooh, 1994;Stevenson,1994).

2.2.1.3 Ecosystem Resilience

Theresilienceofan ecosystemis definedasits capacityto retum to its initial stateafterbeingsubjected
to someform of disturbanceorstress,The importantroleplayedby SOM in determiningtheresilience
ofan ecosystemcan be exemplifiedby acornparisonofthe contentsof chemicalenergyand nutrients
storedwithin the soil organicfractionsin severalecosystems. In temperategrasslands,high organic
matterlevelsarebuiltup in soils asa resultof largebelow-groundadditionsof photosynlhate,iimited
leaching,and slow decompositionrates.Storageof C in suchecosystemsis greaterin the soil thanin
thevegetation(Szabolcs,1994i.The largestoreofchemicalenergyandnutrientscontainedin thesoil
organicfraction offers resistanceto the loss of soil fertility inducedby natural or by agricultural
disturbance. Temperategrasslandsoils,typically Mollisols, haveremainedagriculturallyproducttve
with limitedinputsformany years,despitethemining of energyandnutrientreserves containedwithin
the soil organic fraction (Janzen,1987; Tiessenet al. 1994b). Such systemscan be considered
resilient,at leastinitially, but onemustquestionfor how long suchsystemscan be sustained.This was
exemplifiedby Tiessenet al. (1983),who showedthatratesof organicP mineralizationin a grassland
soil were in excessof crop requirelnentsover the first 60 yearsof agriculturalproduction,but that
B-32 Soil Chemistry

subsequent to 60 years,only the lesslabile,Iow energyproviding forms of organicmatterremained.

and organic P mine.ralization rates decreasedbelow crop demands. In temperate forests, SOM
contents are lcss than those of temperate grasslands and rnore C and nutrients are stored in
abovegroundvegetationthan in the readily availablesoil organicmaterials(Szabolcs,1994).As a
result, the impact of a natural disturbancesuch as fire can significantly deplete ecosystemstoresof
energyand nutrients,and ecosystemrecoveries(resilience)are slow due to low residualcontentsof
SOM and associatednutrienls. Where temperateforests are cleared and agricultural production is
initiated,SOM and nutrientlossesmusf be minimized;however,productionsystemswhich increasc
SOM and nutrient reserves(e.g., crop rotations including legume pastures)can lead to highly
productive and sustainableagriculture.In tropical forest ecosystems,the storageof energy and
nutrientsin vegetationdominates,andtherapid utilizationof plantresiduesby decomposerorganisms
andcyclingof nutrisntsmaintainecosystemstability.This, whencoupledwith thelow storesof energy
andnutrientsin organicmatterof tropicalsoils,indicatesa reducedimportanceof SOM in ecosystem
resilience(Anderson,1995).A comparisonof a temperategrasslandMollisol with a tropical Oxisol
(Tiessenet al. 1994b)demonstratedthe importantcontributionof organicmatter to the resilienceof
the grasslandsoil and its reducedsignificancein the tropicalsoil.

2.2.1.4 Stimulation and Inhibition of Enzyme Activities and Plant and Microtrial Growth
Researchpertainingto the impactsof SOM on plants,microorganismsand enzyme activities has
typicallyutilizedhumic substances (e.g.,humic andfulvic acids)assurrogatesfor SOM. The influence
of humic and fulvic acids,tannins,and melaninson the activity cf variousenzymeswas summarized
by Ladd and Butler (1975), Mtiller-Wegener(1988),and Gianfredaand Bollag (i996), Basedon
earlier studies,Ladd and Butler (1975) concludedthat the effect of humic acids on the activity of
proteolytic enzymes varied and that the mechanism of humic acid-enzyme interaction involved
primarily thecarboxylgroupsof humic acids.Inhibitionof nonproteolyticenzymeactivitiesby humic
acidshavealsobeendemonstrated(SarkarandBollag, 1987).Miiller-Wegener( 1988) indicatedthat
possiblehumic acid-enzymeinteractionswhich could impacton enzymeaclivily included( 1) a direct
interactionof the humic acid with lhe enzymeresulting in a modification of enzyme structureor
changesinthefunctioning of activesites,(2) interferencein theequilibriumof theenzymereactionvia
the humic substances actingas analogsubstrates, and/or(3) a reductionin the availability of cations,
which often act as cofactors required for enzyme catalysis or structural stabilization of the proteln
molecule by fixation on the humic acid molecule.
The effect of soil humic substanceson planl and microbial growth involves the absorption or
adsorptionof the humic speciesand their impacts on biochemical properties at celi walls, cell
membranes,and/or in the cytoplasm.Information on the irnpactsof humic materialsin field studiesis
scarceand often confoundedwith other impactsof humic materialson soil properties(e.g.,CEC,
nutrient status,etc.).The effectsof humic materialson plant growth were reviewed by Chen and Aviad
(1990).Favorableeffectson plantgrowth included(l) increaseduptakeofwaterand germinationrate
of seeds,(2) enhancedgrowth of shootsand roots as assessedby measurementsof length and fresh
andlor dry mass,and (3) increasedroot elongation,number of lateral roots, and root initiation. These
effectsresult from increasedpermeability of cell membranes,increasedchlorophyll content and rates
of photosynthesisand respiration,enhancedprotein synthesisresulting from a stimulation of
ribonucleic acid synthesis,and enhancedenzyme activily (Vaughan and Malcolm, 1985). The
influence of humic substanceson the growth of microorganisms(bacteriaand fungi) also involves a
penetrationandalterationof cell membranes. Addition of humic substances at concentrations S 30 mg
L-t to , nutrient solution increased growth rates in microbial cultures (Visser, 1995)' and in vitro
Soil Oryanic Matter B-33

growth andactivity of nitrifying bacteriahavebeenincreasedby the addition of humic acid (Valdrighti

et a1.,1996;Vailini et al., 1997).

2,2.2 Physical Functions

2.2.2.1 Stabilization of Soil Aggregates

Organic mattsr is consideredimportant to the rnaintenanceof the structural stabiiity of a wide range
of soil typesincludingMollisols, Alfisols, Ultisols and Inceptisols.Its importancetendsto be lessin
OxisolsandAndisols,wherehydrousoxidesplay an importantstabilizingrole, and in self-mulching
soils(e.g.,someVertisols)thatcontainclayswith a high shrinl</swell potential.In soils whereorganic
matteris an important agent binding mineral particlestogether,a hierarchicalarrangementof soil
aggregates existsin which aggregates breakdown in a stepwisemannerasthe magnitudeof an applied
disruptiveforce increases(Tisdall and Oades,1982;OadesandWaters,l99l; Oades,1993).Golchin
et al. (1998) and othsrs have proposedthe existenceof threelevels ofaggregation: (l) the binding
tcgether of clay plates into packets < 20 pm, (2) the binding of clay packets into statrle
microaggregates (20-250 pm), and (3) the binding of stablemicroaggregates into macroaggregates
(> 250 pm).
The importanceand natureof the organicmaterialsassociated with eachlevei of aggregationvary.
At the scaleof packetsof clays, aggregationis primarily dictated by soil mineralogicaland chemical
propertiesimportant in controlling the extent of dispersion, and is often a function of pedological
processes.The binding together of clay packets to form microaggregates occurs via a range of
mechanisms. The dominantmechanismis proposed to involvepolysaccharide-based glues(mucilages
or mucigels)producedby plant roots and soil microorganisms (Ladd et al., 1996), Emersonet al.
(1986)presentedtransmissionelcctronmicrographs showing mucilage located between packetsof
clay plates. Small microaggregates (< 53 pm) held together by humified organic matter and
biologically processed materials are bound together around a particulate organic core (Oades, 1984;
Elliott. 1986;Beareet al., 1994b;Golchin et al., 1994b)to producelargermicroaggregates and small
macroaggregates < 2,000 pm. Macroaggregates > 2,000 pm are stabilized by the presencc of roots,
fungalhyphae and largerfragmenrc of plant residues, which interconnect soil aggregates via bonding
ro aggregatesurfaces, penetration into or through aggregates, and/or physical enmeshment (Tisdall
andOades,1982;Churchman and Foster, 1994; Foster, 1994). Additional informalion pertaining to
the involvementof organic mafter in stabilizing soil structure is presented in Section A, Chapter 7'

2,2.2,2 WaterRetention
Organicmaterialscan influencesoil waterretentiondirectly andindirectly.SOM can absorband hold
substantialquantitie$of water, up to twenty times its mass (Stevenson,1994)' This direct effect'
however,dependson the morphologicalstructureof the organicmaterialsand will not impart any
beneficialeffect to the soil unlessit servesto enhancethe ability of soil to hold water at potentials
within the plant availablerange.Organic matter in the form of surfaceresiduescan also influence
waterretentiondirectly by reducingevaporationand increasingthe infiltration of water'
The indirecteffect of crganiematteron water retentionarisesfiom its impact on soil aggregation
(the
andporesizedisrriburion,andthuson the plantavailablewaterholdingcapacity(AWHC) of soil
poinf). This
differenceberweenvolumetric lvater contentat field capacityand at pennanentwilting
parameterin
effect is best exemplified by the inelusion of soil organicC content as a significant
pedotransfer functionswhich predictporesizedistribution(Vereeckenet al,, 1989;da Silva and Kay,
Siiva and Kay
i 991;Kay et a1.,1997).Equation[2.2] presentsthe pedotransferfunctionderivedby da
B-34 Soil Chemistry

(1997) to describe thc relationship between volumetric water content,0" (mr m-3), and matric
potential;v (MPa), clay content,cL (vo);organicc content,ac (vo);and bulk densiry,BD (Mg mt).
Using this equationKay et al. (1997)calsulatedpredictedchangesin AWHC for soils rangingin clay
conlentfrom 7 to 35o/owhenorganicC contentwas increasedby 0.01 kg kg-'. Increasesin AWHC of
0.039 and 0.020 (m3m{) were obtainedfor the soils with 7 and 35Voclay,respectively,at a relative
bulk densityof 0,?5. Application of the sameequationsto a datasetacquiredby Wegneret al. (1989)
for 80 South Australian red brown earths(Alfisols) showedthat the increasein AWHC inducedby
increasingorganicC contentby 0.01 kg ktr' soil could be expressedby Equation[2.3]. Theseresults
indicate that the presenceof additional organic matter enhancesAWHC of soils; however, the
magnitudeof the increasedecreases with increasingclay content.

0 " = g ( 4 . 1 s + o . o a l n c L + 0 ' 4 ? l n o c + 0 . ? 'Vr l' n BD) ( RB2D=) 0 . 9 4 )

n(-0.5a+0,11llcL+0.02lnOc+0.l0lD 12.21

Changein AWHC = -0.0012(Voclay)

+ 0.055 (R'?=0.82) t2.31

2.2.2.3 Soil Thermal Properties

The typical dark color of SOM contributesto the dark color of surfacemineral soils and can enhance
soil warming and promotebiological processes relatedto temperaturein cooler climates(c.g.,plant
growth and rnineraiizationof C and nutrientscontainedin SOM). However, the presenceof litter
layersor organichorizonscan insulatea soil againstfluctuaticlnsin air temperatureand solarheating.
On severalCanadianforest soils subjectto cold wintersand cool springs,averagesoil temperatures
and the growth of fertilized seedlingswere greaterwhere the litter layers were removed comparedto
where they were left intact (Burgesset al., 1995a,b).Similar effects have been observedin a
comparisonof croppingsystemsthatleavedifferentamountsof oropresidueon the surfaceof mineral
soil (Fortin, 1993).

2.2.3 ChemicalFunctions

2.2,3,1 Cation ExchangeCapacity

Organicmattercontributes25*9AVaof the cationexchangecapacity(CEC) of surfacelayersof
mineralsoilsandpracticallyall of the CEC of peatsandforestlitter andhumuslayers(Stevenson,
1994).The contributionis greatestfor soilswith low clay contentor wherethe clay fractionis
dominated by mineralswith a low chargedensity,suchaskaolinite,andis lowestfor soilswith high
contents of highlychargedmineralssushasvermiculite or smectito. In sandysoils,organicmatter
playsa criticalrolein providingCEC.As a general rule of thumb, each weightpercentage of organic
matterin soilsconuibutesapproximately 3 cmol"kg{ soil to theCEC of neutral pprmanent charge soils
(McBride,1994)andapproximately I cmol..kg-' soil to the CEC of variable charge soils (Oades.
I 989).TheCECoforganicrnatteris derivedprincipallyfromcarboxylfunctionalgroupsbutalsofrom
phenol,enolandimidegroups,andis,therefore, dependent on soilpH.However,because ofpotential
organo-mineral interactionsin soils and the ability of organic matter to complex cations,the
contribution of organic matterto soilCEC values is often much less than could be expected based on
its carboxylcontent.For example, the protonation of carboxylate groups, interaction with positive
ly
charged sitesoninorganic colloids,andcomplexation of Al3*and Fe3* can reduce the abilityof organtc
marterro conrribute to theCECof acidicsoils(McBride,1994).Measurements of theCECof SOM
haveyieldedvaluesrangingfrom 60*300 cmol. kg-l (Leinweber et al., 19931 Stevenson, 1994).
Soil Organic Matter B-35

2.2.3.2 Buffering Capacity and Soil pH

The presenceof weakly acidic chemicalfunctional groupson soil organicmolecules,that can act as
conjugateacid/basepairs,makesSOM an effectivebuffer. The diversity in chemicalcompositionof
the functional groups(e.g.,carboxylic,phenolic,acidic alcoholic,amine,amideand others)provides
organicmatter with the ability to act as a buffer over a wide rangeof soil pH. Jamesand Riha (1986)
reportedbuffer capacitiesof l8-36 and 1.5-3.5 cmol" kg-r (pH unig-r for the organic and mineral
horizons of forest soils, respectively.Stan et al. (1996) obtaineda good correlationbetweenacid
buffer capacityand organicmatter contentfor 29 organic and 87 mineral soil horizons(8, B, and C
horizons)exhibiting buffering capacitiesof 9.8-40.8 and0.1-5.2 cmol" kg-r (pH unit)-1,respectively.
For 59 agriculturalsoil samplestakenfrom the0- I 5 cm layer of cultivatedfields,Curtin et ai. ( 1996)
noted that titratable acidity could be describedby Equation [2.a] in which the terms OC and Clay
representthe soil organic C and clay contentsexpressedin units of kg kg-r soil and ApH is the
referencepH (e.g., 8) minus the initial pH. Assuming that the organic C contentof SOM is 587o,
Equation[2.4], indicatesthat the buffering capacityofferedby organicmatterwas approximately34
cmol"kg-t (pH uni$-' andis an orderof magnitudegreaterthanthat offeredby clay [34 versus3 cmol"
kg-' (pH unitf'1. The averageclay/organicC ratio for the soilsstudiedby Curtin et al. (1996) was'l.91
1, indicating that even though most soils containedmuch more clay than organic C, organic C
accountedfor about two-thirds of the soil buffering capacity.

Titratable acidity to pH 8 = 0.02 + 59 OC ApH + 3.0 Clay ApH R2= 0.95 t2.41

Addition of organicmatterto soil may resultin increasesor decreases in soil pH, dependingon the
influence that the addiiion has on the balanceof the various processesthat consumeand release
protons.A detailedpresentationof thesesoil processesand their ability to releaseor consumeprotons
is givenby van Breemanet al. (1983).Factorswhich needto be consideredincludethe chemicalnature
of the soil and that of the organicmaterialsaddedas well asenvironmentalpropertiesincluding water
contentand extent of leaching.The net effect of adding organicmatterto acidic soils is generallyan
increasein pH values(e.g., Yan et al., 1996; Pockneean{ Sumner, 1997) with the main processes
leadingto the increasebeing ( i ) a decomplexationof metal cations,(2) mineralizationof organicN,
and(3) denitrification.Pockneeand Sumner(1997)found that on the acid Cecil soil, the extentofthe
increasein pH was controlledby the N contentto basiccationcontentratio. The decarboxylationof
organicacids has also beenshown to increasethe pH of acid soils (Yan et al., 1996).Under alkaline
soil conditions,however,theseprocesseswould be ineff'ectiveand would contributeto a reductionin
soil pH as a result of their influence on soil CO, concentrations.The addition of organic matter to
alkalinesoils tendsto acidify themespeciallyunderwaterloggedandleachingconditions(Nelsonand
Oades,1998).The main processes involved in the acidificationof alkalinesoilson additionof organic
materialsinclude(1) mineraliz-ation of organicS andP, (2) mineralizationfollowed by nitrificationof
N, (3) leachingof the mineralizedand nitrified organicN, (4) dissociationof organicligands,and (5)
dissociationof CO, during decomposition.

2.2.3.3 Complexation of Inorganic Cations

The presenceof various functional groups on soil organic materials provides the capacity for
interaction with inorganic cations. The possible interactionscan take the form of simple cation
exchangereactions,such as those between negatively chargedcarboxyl groups and monovalent
cations,or more complex interactionswhere coordinatelinkageswith organic ligands are formed,
such as occur between amino acids and Cu2*.The mechanismsinvolved in the cornplexationof
B-36 Soil Chemistrr

inorganic cations by soil organic nraterialsare discussedin detail in Section B, Chapter 8. Thc
influensethat the complexationof inorganiccationsby soil organicmaterialshas on soil propertlcs
andprocesses includesthefollowing;(i) increasedavailability of insoluble mineral P through
complexationof Fe3*and Alr* in acid soil and Ca!* in calcareoussoil, competition for P adsorptron
sites,and displacementof adsorbcdP (Stevenson , 1994;Cajusteet al., I 996), (2) the releaseof plant
nutrientsthroughthe weatheringof rocksandsoil parentmaterialsby therernovalof structuralcations
from silicateminerals(Tan, 1986;Robertand Berthelin,1986),(3) enhancedavailabilityof trace
olementsin the upperportionof the soil protileas a resultof upwardtranslocation by plantlootsand
subsequentdeposition on the soil surfaceandcomplexationduringresiduedecomposition(Stevenson.
1994),(4) facilitatedadsorptionof organicmaterialsto soilmineralswhich aids in the generationand
or stabilizationof soil structure(Oades, 1984; Emersonet al., 1986), (5) buffering of excessrr.c
concentrations of otherwisetoxic levelsof metalcations(e.g.,Al3*,Cd2t,andPbz*)(Anderson,i995),
and(6) pedogenictranslocationof metalcationsto deepersoil horizons(McKeagueet al., 1986)and
the formation of minerals(Huang and Violantc, 1986).

2.3 QuantifyingSoil OrganicMatter Contents

Soil organic matter contents are difficult to measuredirectly. Most methods measureorganic C
content,and rnultiplythe resultantvaluesby conversionfactorsrangingfrom I .72to2.0 to obtarn
organicmatter contents.The value of the convcrsionfactor usedis determinedby the C contentol
SOM, which is assumedto rangefrom 50 to 587o.Recentstudieshavesuggestedthat the C contentof
SOM is variable and that no single factor is appropriatefor all soils. As a result, researchersare
encouragedto determineand reportorganicC contents.
Methodscurrently usedto estimatesoil organicC contentshavc beenreviewedrecentlyby Nelson
and Sgmmers(1996) and include dry and we! combustionmctht>dsfor total C and dichromatewet
oxidationmethoclsfor organicC. Total C analysesinvolve the completeconvmsionof all C in the soil
to CO, and quantificationof the evolved CO, by variousmeans(e.g., infrared detection,increased
massof an Ascarite trap, or others).Correctionsfor the presenceof inorganicC must be perlormed
when using total C methods if carbonatcsare presentin the soil. Where organic C contentsare
measuredusing dichromate methods (e,g., Walkely and Black, 1934; and subsequentmodified
methods),an excessof dichromateis added.The unuseddichromateis titratedwith Fe(NH.)2(SO,):
6HrO to determinethe amountof dichromateusedduring thereactionand thus the amountof organi;
C present.A basicassumptionof the dichromateprocedureis that soil organicC has a valanceof 0
In addition, dichromateoxidation methodsare subjectto interferencesfrom Ci-, Fe(lI) or Fe(III)
oxicies,and Mn. The presenceof significantamountsof Cl- and Fe2' will lead to an overestilllation.
while thepresenceof MnO, will resultin an undereslimation of organicC levels.The extentof heating
usedin the analysisis also important. Where the heat of dilution or minimal externalheatingis used
completeoxi{ation of soil organic compounds does not occur and correctionfactorsmust be applied
to the resultsof the oxidation procedure. Conection factors ranging from I .0 to 2.86 havebeennoted
in the literatureandan averagevalue of I .3 is recommended if an experimentally tlerivedvalueis not
available(Nelson and Somrners, 1996). Dichromate methods that incorporate extensiveheating
(Tinsley, 1950) do not reguire a conection factor as oxidation of the soil organic C is considereci
complete.Heating has also been implicated in the ability of dichromate oxidation procedurest0
,r.ou*. the organic C contained in carbonized materials (charcoal, chaned plant materials,etc.);
however,the impact of heating is variable and Nelson and Sommers (1996) suggest that recovery is
highly depentlenton rhe charaoteristics of the carbonized materials. Reeent results obtainecl by J
show that the particle size of charcoal is an important factol
Sklemstaa(Personalcommunication)
Soil Organic Matter B-37

determiningits susceptibilityto oxidation by dichromate,with increaseddetectionas particle size

decreased.Of the methodologies currently available, a dry combustion automated analyzer which
measuresCO. evolution with an infrared detector is the prefered methodology for determining soil
organicC, provided accurateestimatesof inorganicC contentscan be obtainedwhererequired.

2.4 FactorsDetermining Soil Organic C Levels

Theamountof organicC containedin a particularsoil is a functionof the balancebetweenthe rate of
depositionof plant residue.s in or on soil and the rateof mineralizationof the residueC by soil biota.
Lossesby erosionor leachingmay be significantin somecases.With the exceptionsof peatlandand
w*etland soils (Histosols),which havebeenestimatsdto accumulate0.l--0,3 Pg C yr-r globally (Post
et al,, | 990),organicC levels in soil do not increaseindefinitelybut rathertendto equilibrium values
dictatedby the soil forming factorsof climate,biota (vegetationand soil organisms),parentmaterial,
time, and topography. During the initial phasesof soil development,a lack of availablenutrients
placesa ceiling on the amountof organicC which canbe fixed by photosyntheticorganisrns.The low
rates of C addition and low nutrient status are not capableof supporting large populations of
decomposerorganisms.Thus, soil organicC accumulatesslowly, aided by mechanismscapableof
biologically stabilizing organic C againstprocessesof decomposition.The mechanismsthrough
whichsoil organicC canbe biologicallystabilizeddependon thecompositionof the soil mineralphase
andthe chemicalstructureof the organicresiduesaddedto the soil. Thus, eachsoil could potentially
offer a different protectivecapacity.With continuedsoil development,organic C content and the
activityof decomposerorganismsincreaseto a point wherea continuedsupply of nutrientsin a plant
availableform is reached.At this point, the rateof organicC synthesisand depositionis much greater
than mineralization,and organic C accumulatesat an exponentialrate. Witit incrcasingorganic C
content,the proportionof potentialsitesof biologicalstabilizationwhich remainsvacantdecreases,
and an increasingproportion of addedorganicC cannotbe biologically stabilized.As a result, the
increasein organicC per unit time procecdsthough an inflectionpoint and then beginsto decrease,
Oncethe capacityfor biological stabilizationofferedby soil mineralcomponentsis approached,the
rateof mineralizationof organicmaterialstendstowardtherateof depositionof freshorganicresidues
andsoil organicC levelsapproachan equilibrium value'
It is important to note that biological protectionrarely equatesto a permanentand complete
removalof organicC from thedecomposingpool,butratherto a reductionin its rateof decornposition
whencomparedto similar rnaterialsexistingin an unprotected state.As theolderprotectedC is slowly
mineralized,its position in the biologically protected pool is replacedwith youngermodern organic
C, but the proportionof such modernorganic C in the protected pool remainslow. It is possiblethat
someforms of soil organicC may bc rendered unavailable to decomposition for prolongedperiods
(potentiallyon a geologictimc scale) through mechanisms such as between
entraptnent layersof clay
plates(Theng et al., 1986) or burning to create charred plant residues and/or charcoal.Piecesol
charcoalselectivelyremovedfrom soil and unassociated with soil mineralshave been shown to have
radiocarbonagesequivalenttoorgreaterthansoilhuminfractions(Pressendaetal.' 1996).Typically'
the proporrionof the total soil organic C held in such more highly stableforms would be minor.
However, in recent soil fractionation/ultravioletoxidation studies, J. Skjemstad (Personal
communication)hasesrirnatedthat charcoalC can accountforO4AVoof the total organicC lbund in
Austraiiansoils.
The progressionof soil organic C content with soil developmentand the magnitude of the
equilibriumlevelof soil organicC will dependon interactionswhich oscurbetweenthe faclorsof soil
formation.Wherecold and watersaturatedsoil conditionspersist,decompositionis confined to slow
B-38 Soil Chemistry

anaerobicprosessesand organic C contentsmay continueto increaseleading to the formation of

Histosols.In sandysoils,theextentof biologicalprotectionofferedby the soil mineralcomponentwill
be much different than that offeredby clay rich soilsandlargedifferencesin organicC contentof the
two texturaiclasscsof soil develop.
An independentevaluationof the influenceof any single soil-forming factor on soil organicC
contentis difficult becauseof the requirementthatall otherfactorsremainconstant.Variationsin the
soil-forming factors experiencedon a landscapescale and the interdependenceof these factors
contributeto the large variability noted for soil organic C contents,even within localized areas.
Computersimulation models ol soil organicC dynamics(e.9.,Parton et a1.,1987) can be usedto
provide valuableinformation pcrtainingto the interactionof soil-forming factorson soil organicC
levelsand thus,ecosystemfunctioning,but field dataare still requiredto validatepredictions(Burke
et al., 1989).
Anadditional factorwhich mustbeconsidered in anexaminationof factorsinfluencingsoil organic
C contentsin disturbedsoils(thoseusedfor agricultureandforestry) is management. Managementcan
induce rapid and drastic changesto equilibrium contentsof soil organic C attainedunder natural
undisturbedconditionsandcompletelyovenidethe influenceof soil-formingfactors.Combiningthis
observationwith early resultspresentedby Jenny( I 930) indicatesthat the relativeimportanceof the
soil-formingfactorson SOM contentcanbe viewedas:management>climate> biota (vegetationand
soil organisms)> topography= parentmaterial> time.

2.4.1 Climate
Climateimpactson soil organicC contentprimarily throughtheeffectsof temperature,m oisture,and
solar radiation on the array and growth rate of plant species,and on the rate of soil organic C
mineralization.Postet al. (1982)found that amountsof soil organicC were positivelyconelatedwith
precipitationand,at a given level of precipitation,negativelycorrelatedwith temperature.In theGreat
Plains of North America, precipitationcontrolsnet primary productivity and temperaturecontrols
ratesof soil organicC mineralization(Partonet al., 1987;Salaet al., 1988;Burke et al., 1989;USDA-
SCS, 1994).Ladd et al. (1985) comparedthe meanlossof raC-labeled plant residuesfrom four soils
in South Australia with thoseobtained by Jenkinson and Ayanaba (1977) for soils in England and
Nigeria and observeda doubling of the rate of substrate C mineralization for an 8-9 "C increasein
meanannualtemperature. An influence of temperature on decomposition can alsobe infened from raC
signaturesof soil organicC, which showeda latitudinalgradicntin thc mean residencetime of soil
organicC (Bird et al., 1996).
The observedtrend of decreasingsoil organicC contentwith increasingtemperatureimplies that
the relativetemperaturesensitivityof decompositionis greaterthanthat of net primary productivity.
Becauseof the stronginteractionsbetweentemperature, wateravailabilityandsubstratequantity,it is
difficult to assessthe temperature dependence of decomposition without confoundingeffects.In a
compilation of dataexfracted from controlled incubation studies where water limitations were avoided
and a conmon substrate was used at all temperatures, Kirschbaum (1995) showedthat the Q1ovalue
of C mineralization from soil was greater than that for net primary productivity developedby Lieth
(1g73),especiallyat temperatures < l5 oC. Increases in temperature, particularly when startingfrom
temperatures < 15 {, will enhance decomposition more than net primary productivity.
Climatehasalsobeenshownto affectthe chemicalstructureof soil organicC. Using pyrolysis-gas
chromatographyto characterizethe chemical structureof soil organic C in a climosequenceof nine
New Zealandsoils, Bracewellet al. (1976)observedsignificantcorrelationsbetweenchangesin the
intensityof peaksin the chromatograms andmeanannualprecipitationandtemperature.By including
both temperatureand precipitation in a regressionanalysis,the resultantregressionline explained
Soil Arganic Matter B-39

9AVoof the variation in chromatogrampeak intensities.Amelung et al. (1997) used ten grassland
samplesoriginatingfrom different climatic zonesof the North American GreatPlains to investigate
theimpactsof meanannualtemperatureand precipitationon the chemicalstructureof soil organicC
usinga combinationof chemicalmethodsand rrC NMR. Mean annualprecipitationwas capableof
accountingfor only lAVoof the variation in alkaline CuO oxidizable lignin. Higher precipitation
tendedto favor an accumulationof polysaccharide C; however,at a given meanannualprecipitation,
polysaccharide C tendedto decreasewith increasingtemperature.Amelung et al. (1997) suggested
rhatthe increasedcontentof polysaccharideC in more humid conditionsmay haveresultedfrom (l)
a positivefeedbackmechanismin which increasedplantproductionenhancedrnicrobialactivily and
soil structuralconditions,thereby offering the potential for stabilizing microbial polysaccharides
within aggregates, and/or (2) an enhancedactivity ofearthwormsincreasedpolysaccharidecontcnt
relativeto the surroundingsoils (Guggenbergeret al., 1995b)and offered organic C some physical
protection against mineralization (Lavelle and Martin, 1992). Accompanying the decreasein
polysaccharideC noted with increasingtemperature,Amelung et al. (1997) noted an increasein
aliphaticC content,Accumulationof alkyl C at high temperaturemay be explainedby ( 1) enhanced
mineralizationof carbohydratesand selectivepreservationof plant or microbially derived alkyl
srrucruresby adsorptiononto clay particles(Baldock et al., 1989, 1992),and/or (2) higher inputs of
plant-derivedalkyl C in plant residuesdue to the presenceof thicker cuticleson plants growing in
warmerclimates.

2.4.2 Soil Mineral ParentMaterialsand Productsof Pedogenesis

The mineral phaseof soils can exert a strong influenceon soil organic C contentsas a result of
mechanismscapableof stabilizing organic materialsagainstbiological attack. As noted above in
Section2.4, eachsoil has a given capacityto protect soil organic C dictatedby the following soil
characteristics: ( 1) the chemicalnatureof soil minerals,(2) the presenceof multivalent cationsand
their ability to form complexcswith organicmoleculesin soils, (3) the adsorptivecapacity of soil
mineralsfor organicmaterialsas governedby pa*icle size and surfacearea,(4) physicalprotection
mechanismswhich restrictaccessof organicmaterialsto biologicalattack.As with other aspcctsof
soil organicC dynamicsaddressedso far in this review, stronginteractionscan exist betweenthese
characteristics (e.g.,the presenceand type of multivalentcationswill undoubtedlybe relatedto the
chemicalnatureof the mineralspresent).

2.4.2.1 Chemical Nature of the Soil Mineral Fraction

An analysisof different soil types indicatesthat soils with high contenls of active CaCO. and
amorphousAl andFe tendto havehigherorganicC contcnts(Sombroeket al., 1993).In a study of the
influenceofsoil propertieson soil organicC genesis,Duchaufour(1976)suggestedthat the presence
of CaCO,in a Rendzinacould stabilizefreshandhumifiedorganicntaterials.Thin carbonatecoatings
visible under stereoscanexamination,and a precipitationof organic molecules induced by Caz*
complexationwereirnplicatedin thestabilizationof freshandhumified organicresidues,respectively,
and helpedto explain the observedimpeclanceof mineralization.Stabilizationof organicC in high
basestatussoilswith lessreactiveor low contentsof CaCO.,resultspredominantlyfrom the fotmation
of Ca organic linkages.In such soils, the initial deconrpositionof plant rcsiduesis rapid' but the
subsequentutilization of initial decompositionproductsis slow leading to higher soil organic C
.ont"ntr. IowerCA{ ratiosandlongerretentiontimes,Soilswith high basestatustypically havehigher
clay contents,aremore fertile, and havegreaterannualvegetativeinputsthan similar low basestatus
soiis.Establishment of causativerelationships betweenbasestatusand organicC contentsmust'
F-40 Soil Chemistrr

therefore,be examinedcarefullybecauseof thepotsntialconfoundingeffectsof increasedvegetative

inputsand stabilizationmechanismsinvolving clay minerals.
Soils derived from volcanic ash(Andisols)aretypically characterizedby large accumulationsol
organicC, high C/1.{ratios, and high allophanecontents.The formation of Al organiccomplexesi:
consideredto be importantto the biologicalprotectionof organicC in Andisols. Boudot et al. (1986.
1988)obtaineda significantcorrelationbetweenthe arnountof nativeC mineralizedfrom 10 Frenclr
highland soils and the contents of amorphousAl and allophane,without observing significanr
correlationswith clay content, exchangeableAF", or crystallineFe oxides. Decreasedorganic C
mineralization rates from rt-labeled organic substratesin allophanic and nonallophanic soil:
amendedwith allophane,relativeto that notedin unamendednonallophanicsoils, also demonstrated
a protectiveeffect of allophanicmaterialon soil organicC {Zunino et al., i982; Boudot et al., 1988
Boudot et al., 1989). Zunino et al. (1982) denronstratedthat the influence of allophane orr
mineralizationof C from an organicsubstratevariedwith the chemicalstructureof the substratc"The
presenceof amorphousFe compoundsandFe3*cationshasbcenshownto havea similar effectto thai
of allophaneand Al3' cations on the mineralizationof C from organic materials; however, the
magnitudeof the protectiveeffect was reduced(Boudot et al., 1989).

2,4.2.2 Impacts of Multivalent Cations

The presenceof multivalentcationsin soil hasimportantimplicationson the behaviorof clays and
organic materials,and the biological availability of organic C. When saturatedwith multivalent
cations,clays remain flocculated,which reducesexposureof organicmaterialsadsorbedonto their
surfaces(Section2.4.2.3)and macromolecularorganicmatcrialsbearingfunctional groupsbecome
more condensed,and thus, less susceptibleto biological attack,The dominant multivalent cations
presentin soilsincludeCa2*andMg2*in neutralandalkalinesoilsandhydroxypolycationsof Fe3nand
Al3* in acidic, ferrallitic and andic soils. A $tabilizingeffect of Ca2*,relative to Na*, on organicC
mineralizationwas effectivelydemonstratedby Sokoloff ( 1938),wherethe extentof mirleralization
andsolubility of organicC in two soilswasreducedby additionof Caz*saltsandenhancedby addition
of Na*salts.Otherstudieshavealsoshownadecrcasedsolubility of organicC in the presenceof Ca:'
(Muneer and Oades 1989c) and reducedmineralizationof native organic materials and organic
substrates on additionof Ca2*inincubationstudies(Linhares,1977;Muneerand Oades,1989a,b).in
such studies,the questionremainedas to whetherthe effect of Ca2*addition on mineralizableC
resultedfram an indirect effect on colloidal dispersitrility or from a direct effect of Ca?*complexation
on the biodegradability of organic molecules'
A directeffect of multivalentcationcomplexationon biodegradabilityin soil wasdemonstrated b1
the following results:(l) areducedoxygenabsorptionon incubation of humic acidssaturated with
Ca2*.Al3', orFe3*in the samesoil, relativetothatnotedforNa"-saturated humicacids(JusteandDeias.
19?0; Justeet al., l9?5), (2) an increasedstability of Al3* and Fe3* forms of plant and microbial
polysaccharides(Martin et al., 1966, 19?2), and (3) a three-fold increase in the amount of C
mineralized from an organic soil after replacing Ca?*cations with K' during a 25-week incubation
(Gaiffe et al., 1984).Indirect evidencefor the involvementof cations in the accumulation of organic
C in soilscanalsobeobtainedthroughacomparison ofthe organic C contents ofa varietyofsoil types.
C contents of 29 Australian great soil
Using data derived from Spain et al. (1983) for the organic
grouir, Oades (1988) showed that, excluding soils subject to waterlogging, there was a positive
correlationbetweenorganic C contentsand either high basestatusor the presenceof substantial
which
contentsof Al and Fe oiides. Of interestwas the comparisonof siliceous and calcareoussands
C content in the presence of Caz*-
have little or no clay, but indicate an increasedsoil organic
containing mineral fractions (< 0.5-I.57o versus 1.5-> 47o organic C, respectively')
Soil Organic Matter B-41

2.4.2,3 Adsorption of Organic Materials onto Mineral Surfaces

Clay particles provide a reactive surface onto which organic materials can be adsorbed and it is
generallyacceptedthat such adsorptionreactionsprovids a mechanismof stabilizingsoil organicC
againstmicrobial attack.Correlationsbetweensoil organicC and clay contentshave beenobserved
(Schimelet al., 1985a,b;Spain, 1990; Feller et al., l99l) and the various interactionsbetweensoil
claysandorganicmateriaishavebeensummarizrdby Oades( 1989),Suchinteractionsareprincipally
definedby thechemicalnatureof organicmaterials(functionalgroupcontent,molecularsize,etc.)and
the type of clay mineral (kaolinite, illite, smectite,etc.), Numerous studics utilizing isotopically
labeled organic substrateshave shown a positive relationshipbetween the contents of residual
substrateC and soil clay content(Amato and Ladd, 1992).
ln a field expcrimentwhere raClabeledplant residueswereaddedto four cultivatedsoils varying
in clay content(542Vo)buthaving similar clay mineralogy,climatic conditions,and no otherorganic
inputs,theamountsof residualraCand totalorganicC in thetopsoil(0-10 cm) remainingafterB years
of decompositionwerenearlyproportionalto soii clay content(Ladd et al., 1985).Saggaret al. (1996)
'aC-labeled
completeda similar studyin which the decompositionof ryegrasswas monitoredover six
yearsin four soils having variableclay content(1G60Vo)and clay mineralogy.The mean residence
time of the roC-labeled ryegrasswas not relatedto clay contentbui raiherto surfaceareaasmeasured
by adsolptionof p-nitrophenol. The increasein meanresidencetime with increasingsoil surfacearea
suggested that the protectivecapacityof the soilstowardtransformedmetabolitesderivedfrom plant
residueswasprincipally controlledby adsorptiononto soil surfaces.Sincethe datapresentedby Ladd
et al. ( 1985)werederivedfrom soilswith a similarclay mineralogy,soil surfaceareaswould havebeen
well conelatedwith clay content.The importanceof availablesurfaceareawas also suggestedby the
resultsofSgrensen(1972, i975)wheretheadditionofhighsurfaceareamontmorillonitetoasoil/sand
mixturestabilizedmicrobialrnetabolites, but additionof low surfaceareakaolinitehadlittle influence.
Theseresultssuggestthat the potential protsctive capacityof soil clay rnineralsis more a function of
the surfaceareaavailablefor adsorptionof organic C than the actualamount of clay.

2.4.2.4 Physical Protection within soil Matrix offered by soil Architecture

The architectureor structural condition cf a soil can exert significant conlrol over processesof
biological decomposition by limiting the accessibility of soil organic C to decomposer
microorganismsand of microorganismsto their faunal predators.This iimitation results from the
ability of clays ro encapsulateorganicmaterials(Tisdall and Oades,1982),the burial of organicC
within aggregates (Golchin et al., 1994b,1997b),andthe entrapmentof organicC within small pores
(Elliou and Coleman, 1988).As outlined b,vvan Veen and Kuikman (1990) and Hassink (1992),
evidenceof the importanceof theseprocessesin the protectionof organicC in soils can be inferred
from the following observations:(1) a fasterturnoverrate of organic substratesin liquid microbial
culturesrelativeto that of similar substratesin mineralsoils,(2) an enhancedmineralizationof C and
N when soils aredisruptedprior to incubation,and (3) a more rapid mineralizationof organicC and
plant residuesin sandysoils than clay soils.
A continuumof pore sizesexist in soils,startingwitlr largemacropores(> 20 pm) and decreasing
to micropores(< 0. 1Lrm).Kilbertus( 1980)suggested thatbacteriacanonly enterpores> 3 pm, which
suggest;that a significant proportion of the soil pore spacemay not be accessibleto microbial
d"ii*pos"rr. Organic materials aclsorbsdonto clay particlescontainedin pores< 3 pm would only
be decompo.sed as a rcsult of diffusion of extracellular enzymes releasedby microorganisms.With
increasingsoil clay content, the proportion of the total soil pore spacecontainedin micropores
increases,and the potential for stabilization due to the exclusion of soil microorganismsincreases.
This conceptof exclusion can be extended to the predation of microorganisms by soil fauna'Van der
B-42 Soil Chemistrl

Linden et al. (1989) suggestedthat Protozoaand nematodesare excludedfrom pores < 5 pm and
< 30 pm, respectiveiy. Killham et al. (1993)showedthatalthoughplacingglucoseinto pores< 6 prn
or < 30 pm did not impact on the rate of glucose decomposition,the turnover of glucose C
incorporatedinto the microbial biomasswas slowerwhere glucosewas only addedto pores< 6 pm.
The ability of clay particles to adsorb organic materials can also contritrute to a biological
stabifizationof soil organicC throughan encapsulation of organicresiduesin soils and the formatron
ofstableaggregates. Encapsulation ofparticulateorganicresiduesin soilsnot only placesaphysicai
barricr betweendecomposerorganismsindigenousto soils and substrates,but can also can limit the
movcmentof waterand O, to sitesof potentiallyactivedecomposition. A similarsituationdevelops
within soil aggregates.Relative to the larger pores betweenaggregates,the smaller pores within
aggregates aremore likely to remainfilled with waterduring drying events,and therefore,restrict O.
movernentinto the aggregate.The presenceof organic corcs in aggregates(Beare et al., l994a,b;
Golchin et al. 1994, 1997a,b)will scrveto increasethis effect by enhancing O, consumptionwithin
the aggregate.It has beenfbund that anaerobicconditionscan exist in the core of moist aggregates
evenunderwell-aerated conditions(Sexstone et al., 1985).In nativegrasslands,AmelungandZech
( 1996)demonstratedthat the exterior0.5 mm of > 2 mm diameterpedscontainedlessorganicC and
had a higher CA{ ratio, lesslignin, and more microbial derived saccharidesthan ped interiors.The
organicC associatedwith ped surfaces,therefore,appearedto turn over more rapidly, and exhibit a
greaterdegreeof decompositionthanthat containedwithin peds.

2,4.3 Biota: Vegetationand Soil Organisms

2,4.3.1 Vegetative Inputs: Variations acrossand within Ecosystems

Vegetation can influence soil organic C levels as a result of the amount, placement and
biodegradability(chcmicalrecalcitrance)ofplant residuesreturnedto the soil. The greatesteffectsof
vegetationon soil organic C contentsare confinedto the A horizon. Concentrationsof organic C
detectedbelow the A horizon result from pedogenicprocesses,which occur over much longer time
scalesthanthe lifetime of currentvegetation.Volkoff and Ceni (1988)showedthat for Braziliansoil
profiles,currentvegetativecover was only in direct equilibrium with topsoil (A horizon) organicC.
while that in subsoilswas largely unaffectedby the natureof vegetativecover. Once the organicC
movestodepth (e.g.,argillic or spodichorizons),it becomeslessaccessibleto decomposerorganisms.
as exemplifiedby the increasedradiocarbonagesofsoil with depth (Pressendaet al', 1996).
Scharpenseelct al. (1992) provided eslimatesof the amount of organic C contained in the
vegetation,soil, and annuallitterfall associated with various ecosystems(Fig.2.1). Across the
tropical,temperate,and boreal forests, a continuous decreasein the amountof plant biomassandlitter
C is noted,with little change in the amount of organic C storedin soils.The decreasein the ratio of
plant biomassC: soil organic C was associated with an increasein turnover Limefrom l8 to 60 yr
Presumably,most of this variation was related to theeffect of temperatureon litterfall decomposition.
however,significantchanges in litterfall quality and morphology arealsoevident.On the basisof the
informationreviewed in Section 2.4.1, the amount of residue returned to the soil under similar types
of vegetationappears to be a function of climatic factors, principally the amount of precipitation;
however,this will depend on the nature of the factor most limiting plant growth. Where amplewater
is available,the amount of residues returned to the soil may be a function of someother factor suchas
nutrient supply. Where climatic and soil factors are constant, residue placement may become
important.A ro*pariron of the amounts of organic C contained in the plant biomassand soils of
temperategrasslandand forest ecosystems reveals that despite a much smaller amount of plant
biomassin the grassland,annual litter C inputs and soil organic C contents were approximately twice
Soit Organic Matter B-43

E00 -i
700
fi zo.ooo 600 c
50

! rs,ooo
5fi)
a
d .t00
U
.9 10,000 300
200
5 s,ooo
r00
0
Tslper3tc
foresl
Plgnt biomassC 1.38 1.55 0.60 0.-13
Soil orgenic C
T||r$ovcr tim€
(y{)
Fig.2.1 Variations
in meansoilorganic
C contents,plantbiomass
C contents
andrateof litterdeposition
in various
[Drawnfromdataof Scharpenseel
ecosystems et al.,i9921

that of the forests (Fig.2-1). The occurrenceof deep organic rich mineral horizons in temperate
grasslandsoils(c.g.,Mollisols), in comparisonto the concentrationof organicmaterialsin litter layers
in borealforestsoil (e.g.,Spodosols),is an exampleofthe influencewhich vegetationcanhaveon soil
organicC contentand distributionwithin the soil profile. The apparentlargerinput of belowground
residuesin grasslandsoils, comparedto forest soils, placesorganicC in closeproximity to the soil
mineralcomponents,therebyenhancingthe potentialfor biologicalstabilizationvia the mechanisms
discussedin Section2.4.2.Turnovertimesin grasslandsoilsaregreaterthanin forestsoils (34 versus
24 yr, respectively).
The fateof surfacedepositedresiduesdependson theactivity of soil microorganismsandfaunaand
their ability to mix theseresiduesinto the surfacemineralhorizons.In well-drainedsoils with high Ca
status,the activity of earthwormsand other soil faunais high, leadingto a mixing of organicresidues
throughprocessesof particle size diminution, ingestionand casting,and bioturbation.Under such
conditions,a mull type humuslayer is formed andlitter layersdo not develop.Plantresiduesand their
decompositionproductsare intimately mixed with soil mineral particles,which facilitatespotential
biologicalstabilizationthroughorganomineral interactions(Section2.4.2).Soils low in Ca do not
supportas active soil faunal populationsand plant residuestend to accumulateon the soil surface
forming organic rich, mor-type humus layers. Within mor-type humus little potential exists for
biological stabilization other than that due to the chemical recalcitranceof highly decomposed
residues.The intermediate form of humus is referred to as a moder.

2.4.3.2 Composition of Plant Materials: The Parent Material for Soil Organic C
Plantmaterialscanbe viewedasthe parentmaterialfor soil organicC in much the samemannerasone
views primary mineralsasthe parentmaterialsof soil mineralcomponents.Plantmaterialsarealtered
by soil fauna and microorganisms,predominantlyafter depositionin or on the soil, resulting in
changesin the original chemicalstructureand in the synthesisof new compounds,just as somesoil
mineralsdissolveandothersprecipitateduring pedogenesis. An understandingof the chemicalnature
of plant materialsis, therefore,importantto studiesof soil organicC genesisand composition.
Plant materialsconsistof a rangeof different compoundsvarying in concentrationacrossplant
species,plant components(e.g.,conducting,supportingor photosynthetictissues),growth stages,and
space(distribution in the landscape).Plant cells can be divided up into three components:the
B-44 Soil Chemistn

cytoplasm,cell membranesand cell walls. The cytoplasmcontainsthe simple sugars,organicacids

aminoacids,andenzymesessentialto maintainmetabolicactivity.Cell membranesconsistof globular
proteins embedded within a lipid bilayer. Plant cell-wall componentsinclude hemicelluloses.
celluloses,lignins, proteins,cuticularand root waxes.Oades(1989)presentedthe following average
contentsfor the major typesof organicC in plant residues:(l) extractablematerialsincluding water
extractables(simplesugars,amino acidsandorganicacids)andorganicsolventextractables(free anC
boundalkyl moleculesincludingfats,oils andwaxes)- 200 g kg-r,(2) hemicelluloses- 200 g kg-', (:
celluloses- 300 g kg-', (4) lignins -2A0 e kg-t, and (5) proteins- 60 g kg-'.
The organiccomponentsof plant cell walls accountfor the majority of the massof plant residues
depositedin soils. Carbohydratestructuresconsist mainly of the polysaccharidescellulose ani
hemicellulose.Cellulose is the primary componentof cell walls with a dominant structureof D-
glucopyranoseresidueslinked into a polymer via p-1,4 linkages(Fig.2.2). Cellulosecan exist in
either a crystalline or amorphousstateasindicatedby X-ray diffraction (Atalla and van der Hart, 198.1'
and solid-stater3Cnuclearmagneticresonance(van der Hart and Atalla, 1984).The crystallinestare
is more highly resistantto microbial andenzymaticdegradationthanthe amorphousform (Ljungdahi
and Eriksson, 1985).Hemicelluloseis defined as the polysaccharides extractablein alkali solution
The hemicellulosesexist as linear and branchedpolymersof D-xylose,L-arabinose,D-mannose,D-
glucose,D-galactose,andD-glucuronicacidmonomers,which may be acetylatedor methylated.Most
hemicellulosesarecomposedof 2 to 6 of thesemonomerslinked togetherprimarilyvia a p-1,4 linkage
backboneas shown inFig.2.2 for pectin, a glucuronicacid polymer.
Lignin representsthe secondmost abundantorganiccompoundin plant residues,and accountsfor
approximately5Voof the mass of grassesand up 6 3AVoof the mass of hardwood forest species
(Haider, 1992).The basic building block of lignin, coumaryl alcohol, can be substitutedwith zero.

Ccflulo* Nonc.llul6k pohrft ch.ridct (H.nLell!lor.) Chifin

Ellucopyiln* Giduct linked by F-l/ linkrgs sith F-l,{ linkig.!
Prtin wirh F.l.l linkrr.r N-s.tylgluouminr

Ermph! of FGI linltd llgnint

Llgnio pc!ffi Syrir$il FHydotph.nol

+*",.,,$o.",
Cutin rnd Subartn Mffir

oll

flocn{cq)rcl|-cH{cl{)toon Hocqcq)fHcH(c4),cooH

o{
Fig.2.2 Representativechemical structuresof the organicmacromoleculesfound in plant and microbial residues
enteringthe soil.
Soil Organic Matter B-45

one, or two methoxyl groups at the C-3 and C-5 positions on the benzenering to produce the p-
hydroxyphenol,guaiacyland syringyl lignin monomericunits,respectively{Fig.Z.2). The units are
then linked together by more than 12 possible interunit linkages based on C-O or C-C bonds
(McDougall et al., 1993).The major interunitlinkage,accountingfor about6OVo of the linkages,is the
p-O-4 linkage depicted in Fig. 2.2 for the three lignin monomeric units. The nature of the lignin
molcculechangeswith plant type:softwoods(gymnosperms)aredominatedby guaiacyl-based lignrn,
hardwoods(angiosperms)containa mixture of guaiacyl-and syringyl-basedlignin, and grassesare
dominatedby syringyl lignin. Resultspresentedby Hedgeset al. (1985) suggestedthat suchchanges
in lignin compositioncan affect its biodegradability,with syringyl lignin being more susceptibleto
decomposition thanguaiacyllignin.
The protein and water solublecomponentsof plant residues,unlessstabilizedagainstbiological
attack,provide a readily decomposablesubstratecapableof supplying the chemical energy and
nutrientsrequired to drive soil biological processes.Enzymaticcleavageof the peptidelinkagesto
form amino acids and mineralization of amino acid N to form NHo* provide sources of N for soil
biologicalprocesses,and the abiotic chemicalprocesses, to be discussedsubsequently.
Alkyl componentsof plant materialsincludefreeandboundIipids,polyesters,and nonsaponifiable
alkyl C-dominatedbiopolymers.Freeandboundlipids represent a heterogeneous groupof neutraland
polar molecules which are classified together basedon their solubility in organic solvents (Tegelaar
et al., 1989).The neutralcomponentconsistsoftriacylglycerols and waxes,which serve to protect
external plant surfacesand to store energy. The polar component is dominated by the esterified fatty
acidsfound in cell membranes.Insolublepolyestersderived from hydroxy fatty acids are found in
cutin in plant cuticlesand in suberinin roots.Cutin and suberinare composedof various long-chain
(C,oand C,r) substitutedfatty acids.The main substituentgroup is hydroxyl with lesseramountsof
epoxy,ketoneandcarboxylgroupsalsopresent(Holloway, 1982).Twoexamplesofcutinandsuberin
monomers are presentedin Fig. 2.2 and Tegelaaret al. (1989) have presentedfigures showing
additionalmonomericchemicalstructuresand a proposedmodel of the structureof intact cutin and
sutrerin. Plant cuticles and roots have also been shown to contain nonsaponifiablealiphatic
biopolymers which have been labeled cutan and suberan(Nip et al., 1986a,b,1987). Cutan and
suberanareconsideredsimilar to cutin andsuberinwith the exceptionthat they arehighly crosslinked
by nonesterbonds.
In orderto assessthe influenceof plantresiduecompositionon decompositionandmineralization,
it is essentialto removeotherconfoundingeffectssuchasclimatic, soil and biological parameters.In
field studies,this can be accomplishedby examiningdecompositionof all residuesof interestat a
single site. Vedrova (1991) assessedthe impact of forest specieson litter decompositionrates by
placinglitter collectedfrom eachspecieson small plots locatedwithin a singleunforestedsite.Mean
ratesof mineralizationmeasuredfor cedar,pine, larch, spruce,aspen,and birch litter over - 2 years
w e r e 1 . 9 3 ,1 . 5 7 ,1 . 8 5 , 2 . 2 A , 2 . 5 6 , a n d 2 . 5m7 g C g - ' l i t t e r C d - ' , r e s p e c t i v e l yA. l i m i t a t i o no f s u c h
studiesis demonstrated,however,by the work of Elliott et al. (1992),in which the decompositionof
four different forestlitters (mixed hardwood,red pine, beech,and hemlock)was examinedin eachof
the oril four forest types.The ratesof decompositionwere principally a function of litter type, with
mixed hardwood litter decomposingthe fastestand hemlock litter the slowest.However, with the
exceptionof the mixed hardwoodlitter, decompositionratesof the individual litter typeswerehighest
when they were placed in the forest type from which they were derived (i.e., decompositionof the
hemlock litter was greatestin the hemlock forest).This interactionbetween litter type and foresttype
suggeststhat decompositionpathwaysin any given ecosystemmay be tailored to the type of litter
deposited.Thus, the resultsof decompositionstudieswherelitters areremovedfrom their ecosystem
B-46 Soil Chemistry

of origin, or where the community structure of the decomposerorganismsis altered, may nol
accuratelyreflect the relativeeffectsofresidue compositionon decomposibility.

2.4.3.3 Relative ImpacG of Soil Fauna and Microorganisms

Therequirementof soil organismsforchemicalenergyandnutrientsdrivesprocesses of heterotrophic
decompositionin soils. which account for the major pathways through which soil organic C is
mineralized.Atriotic chemicaloxidation is unlikely to accountfor > ZOVoof total C mineralization
(Moorehead and Reynolds, 1989) and more often accounts for < 5Vo (Lavelle et a1., 1993).
Microorganismsare the major contributorsto soil respirationand areresponsiblefor 80-95% of the
mineralization of C. Hassink et al. (1994) caiculated that the contribution of the fauna to C
mineralization in two sandy and two loam grasslandsoils ranged from 5-73Vo of the total C
mineralization.The patternof C mineralizationby the soil faunathroughtime, notedby Hassinket al.
(1994),differedfrom thatof total C mineralization,suggestingthattheactivity of the soil faunadid not
contribute substantiallyto the differences in total C mineralizationobservedbetween the soils.
Hassinket al. ( | 993) concludedthat soil protozoaand nematodesdid not significantly influencesoil
C mineralization despite a positive responseof bacterivorousnematodeson the amount of N
mineralized.Severalother studieshave shown that soil faunaenhancednutrientmineralization,and
had both positiveand negativeeffectson soil organicC mineralization(Griffiths, 1994;Kajak, i 995;
Alphei et al., 1996).In a study including protozoa,nematodesand earthworms,Alphei et al. (1996)
notedthat none ofthe fauna studiedsignificantly affectedbasalrespiration.

The role of soil fauna in decompositionprocessesshould not be based only on their direct
contributionto C mineralization.Soil fauna also act to reducethe particle size of litter, distributeit
within the soil, Lransportotherwiseimmobile microorganismsto new siteswithin the soil matrix, and
prime microorganismactivitiesby the productionof easilymetabolizablesubstrates(e-g.,earthworm
intestinal mucus). In so doing, soil fauna generally snhance microbial activity and rates of
decomposition.Soil conditionswhich limit (e.g.,water saturationand the developmentof anaerobic
conditions)or enhance(e.g.,tillage or installationof drainsin imperfectlydrainedsoils) the activity
of soil microorganismsor fauna will also impact significantly on organicC mineralizationratesand
thus,alter soil organicC levels,

2.4,3.4 Composition of the Microbial Community

The populationof decomposermicroorganismsin soil is extensive;densitiesup to 1010bacteriaand
severalkm of fungal hyphaeper gram of soil havebeenmeasuredin a wide rangeof soils (Lavelle et
al., 1993).Asaresultofthediversityofdecomposerorganisms,theexistenceofinteractionsbetween
specific types of organic residue and speciesof decomposerorganismscan have pronouncedeffects
on the chemicalstructureandbiological availabilityof residualorganicmaterials.The decomposition
of woody materialsprovides an excellenl example of how the speciescomposition of the decomposer
population can influence the chemical nature of decomposition products. Laboratory incubations of
Eucryphia cordifolia wood with a brown rot fungus (unidentifiedspecies)and a white rot fungus
{Ganodermaaustrale)showed a more selectiveutilization of carbohydrateC by the brown rot fungus
and a delignificationby the white rot fungus (Martinezet al. l99l). Using the samewhite rot fungus
in a solid-statefermentationprocedurewith beechwood, Martinezetal, (1991) notedlittle changein
thechemicalcompositionof the wood, despitea36%amassloss.Barrassaet al. (1992)obtainedsimilar
resultsin an ultrastructuralstudy.Selectivedelignificationof Laureliaphilippiana wood by the white
rot fungus Phlevia chrysocrea was noted, but decomposition of the same wood by Ganodertna
Soil Organic Matter B-47

australeresvltedinincreasedlignin contents.The selectivedegradationofcarbohydratesby brown rot

fungi appearsto occur independently ofthe fungal or wood speciesinvolved. However, the presence
ofa selectiveor nonselectivedegradationprocessfor white rot fungi appearsto dependon interactions
betweenthe speciesof fungus and wood. Under anaerobicconditions, the activity of obligate aerobes
such as wood degrading fungi is limited and bacterial decomposition processes dominate. In
examinations of buried woods, it has been found that decomposition processesinvariably result in a
preferential utilization ofcarbohydrates and a concentrationoflignin (Batesand Hatcher, 1989; Bates
et al., l99l ). Suchdataindicate that changesin speciescomposition of the decomposercommunity can
significantly atter the decomposition processesand thus, rates of accumulation or loss of organic C
from soils. At present,insufficient data exist to extend the results obtained for woody residuesmore
generallyto nonwoody organic materials,but the governing principle would be expectedto be similar.

2.4.3.5 Relationship Between Organic Residue Composition and Chemical Recalcitrance

All organic C in soils can serve as a substrate.In addition to the potential mechanismsof biological
stabilization of organic materials offered by the soil mineral fraction, chemical structure can also
impart a degree of chemical recalcitrance.Rates of decomposition of known organic substancesin
soils were reviewed by Paul and van Veen ( 1978).Although variations in decompositionratesfor any
single substrate were evident as a result of differences in soils and incubation conditions, simple
organicmoleculesand monomericcompoundsdecomposedmost rapidly. Oades(1989) showedthat
the extent and rate ofmineralization ofC for a seriesofpolysaccharides (glucose,dextran, cellulose)
and a fungal polysaccharide)decreasedwith increasingmolecular complexity and branching. Similar
results were obtained by Martin and Haider (1975) for the mineralization of C from specifically taC-
labeledbenzoic and caffeic acid monomersand polymers. C mineralization was most extensivefrom
carboxylic acid groups, less extensivefrom the aromatic ring C of the monomers,and least extensive
from the polymeric aromatic ring C. Of the polymeric materialscontained in plant residues,lignin and
otherpolyphenolic C and aliphatic C appearto be the most recalcitrant,but asdiscussedin the previous
section, the stability of lignin C will be related to the species composition of the decomposer
community.
Many studies have demonstrated a relationship between decomposition and plant residue
characteristics thoughtto be indicativeof residuequality (Edmonsand Thomas,1995;Hobbie,1996,
Cortez et al., 1996; Agren and Bosatta, 1996). Included in these residue characteristicsare N
concentration,C:N ratios, lignin and/orpolyphenolconcentration,lignin:N ratios,and acid soluble
carbohydrates. In a laboratory incubation experiment, examining the impact of temperature on
decomposition of six speciesof tundra vegetation, patternsof decomposition were better correlated
with substrateC compositionthan nutrient;masslosseswerepositively correlatedwith acid-soluble
carbohydrate content and negatively correlated with lignin content (Hobbie, 1996). In a separate
incubation study, massloss from four types of one-year-old mediterraneanratio of the litter (Cortez
et al., 1996; Agren and Bosatta, 1996).Included in theseresiduecharacteristicsare N concentration,
C:N ratios, lignin and/or polyphenol concentration,ligninA.I ratios and acid soluble carbohydrates.In
a laboratory incubation experiment, examining the impact of temperatureon decomposition of six
species of tundra vegetation, patterns of decomposition were better correlated with substrate C
composition than nutrient; mass loss from four types of one year old Mediterranean deciduous leaf
litter as well correlated with the 7oN, C:N ratio, lignin concentration and lignin:N ratio of the litter
(Cortexetal.,1996).AgrenandBosatta(1996)foundthattheproportionsofextractable,acidsoluble,
and acid insolubleC obtainedfrom a conventionalchemicalfractionationcould be usedto assessthe
quality of forest litter, particularly when the acid insoluble fraction did not dominate. During the
decompisitionof plant residues,significantchangesin chemicalcompositionof residualC areevident
B-48 Soil Chemistrt

( B a l d o c k e t a l .1
, 9 9 7 )I.n r e s p o n s e t o s u c h c h a n g e s , B e r g a n d S(t1a9a8f 0 ) p r o p o s e d a m o d e l o
l i fu e r
decay in which decompositionwas controlled initially by N content,but subsequently,by lignin
concentration.This was supportedby the resultsof EdmondsandThomas( 1995),which showedthat
organic C mineralizationrates from green needlesof westernhemlock and pacific silver fir were
initally similar, but becamemore a function of litter chemistry(e.9.,lignin:N ratio) asdecomposition
progressed.

2.4.4 Topography
Topographyexertsits major controlover soil organicC contentsthrougha modificationof climateand
soil texturalfactors,and throughits impactson the redistributionof water within a landscape.Soils in
downslopepositionsareoften wetter,havewarmeraveragetemperatures, andhavefiner texturesthan
soilsin upslopepositionsor at thetop of knolls.Burkeet al.,(1995)examinedtheextentto which soil
organicC varied at a landscapescaleat two sitesdiffering in soil texture,but having similar climatic
characteristics.Burke et al. (1995)notedincreased organicC contents(andclay and silt contents)in
downslopepositionsrelative to the summits at both sites.Such a finding has been attributedto the
downslope movement of organic C and organic rich clay (Reiners, 1983). However, additional
gradientsin availablewater along slopes,especiallyin water limited systems,influenceplant
production(Petersonet al., 1988)with greaterbiomassinputs and a greaterpotentialbiological
stabilizationof organicC via higherclay contentsat the baseof slopes.Whereexcessivewatercxists,
drainageof depressionsin the landscapecan be restricted,leadingto the developmentof anaerobic
conditions and preservationof organic C relative to the better drained higher landscapeelements
during wetter times of the year.

2.4.5 Land Management Practices

Paustianet al. (1997) have comprehensively reviewedthe influenceof agriculturalmanagement
practiceson soil organicC levels.The influenceof forestrymanagementpracticeshasbeenreviewed
by Johnson(1992).The most dramaticinfluenceof agriculturalpracticesoccurswhen soils are first
brought into production. Typically, soil organic C levels decreasefor the first few years after
cultivation and thenstabilizeat a new equilibrium level which is dictatedprincipally by thc ability of
the soil to stabilize organic C and amount, quality, and distribution of plant residuesinputs. For
example,28-59Voof the soil C was lost following 30 to 43 yr of croppingat 1 I siteswithin the North
American prairies(Haaset al., 1957).The following characteristicsof cerealproductionsystems,in
comparisonto thoseof nativegrasslands, helpto explainthe observedlossesof soil organicC induced
by cultivation: (1) 807olower ailocationof organicC to soils (Buyanovskyet al., 1987),(2) reduced
below ground allocation of photosynthate(Andersonand Coleman, 1985),(3) enhancedaggregate
disruptionandexposureof physicallyprotectedorganicC due to cultivation(seeSection2.4.2.4),and
(4) enhancedratesof decompositionof availableorganicC substratesdue to more favorableabiotic
conditions(e.g.,aeration,temperatureand water content).
The intensitywith which soil is cultivatedcan impact both the total amountof soil organicC and
its distributionwith soil depth.No{ill systemstend to concentrateresidueinputsat the soil surfaceand
generally enhancesoil organic C and N contentsin soil surface layers. Therefore, to accurately
evaluatethe influenceof tillage practiceson soil organicC stores,it is importantto sampleat leastto
the depth of tillage, and preferably,deeper.Paustianet al. (1997) presenteddata from a number of
long-termfield trails indicatingthat soil organicC retentionis typcally enhancedunderno-till relative
to more intensiveconventionaltillage systems.The selectionof annualcrops and the inclusion of
annualand perennialpasturesor mechanicalfallows in rotation with annualcrops can significantly
Soil Orpanic Matter B-49

impact on soil organic C levels. In a long-term crop rotation trial locatedat the Waite Institute in
Australia, soil organic C contents have increasedunder permanentpasture and declined to varying
degreesunder cropping systems,with the extent of the delcine being relatedto the intensity of soil
cultivation (Tisdall and Oades, 1982).Field trials set up to examine the impact of fertilizer additions
on soil organic C contenthaverevealedthat the addition ofN fertilizers typically enhancessoil organic
C contents.Explanatorymechanismssuggestthat N fertilizer additionsresult in a greaterreturn of
plantresiduesto soils,a reductionin decompositionratesdueto enhancedsoil drying (Andr6n, 1987),
a promotion of soil acidification (Thurstonet al., 1976),a repressionof lignilytic enzymes,and a
formation of recalcitrant humic materials through a reaction of amino acides with humic precursors
( F o g .1 9 8 8 ) .
In tropical systems,the establishmentof pasturesafterclearingof forestsis becomingincreasingly
widespread(Sombroek et al., 1993).Pastureestablishmentimmediately after deforestation,using
specieswith high proportions of below-groundbiomass,may increasesoil organic C contentsas
demonstratedin the Brazilian Amazon (SerrAoet al., 1979),Latin America (Ligel, 1992) and East
Africa (Boonman, 1993).If pasturesare installed after one or more cycles of shifting cultivation,
productivity is low and soil organicC levels remain low (Sombroeket al., 1993).

2.5 ChemicalStructure of Soil Organic Matter

2.5.1 Characterizing the Chemical Structure of Soil Organic C

2.5.1.1 Wet Chemical Methods of Extraction and Characterization

Classicalapproachesto chemicalcharacterizationof soil organicC involved the use of water- and
organic solvent-basedchemical extractants,and various degradativeproceduresconsideredselective
in their attack on specific molecular structures.After the removal of macroorganic materials via
sieving or flotation and extraction of dissolvedorganic C (DOC), the remaining organic C was
partitionedinto humic substancesand nonhumic biomoleculres.The distinction betweenthesetwo
forms of organicC is basedon structuralchemistry(Table2.2).Severalof the potentialmethodologies
capableof being used to quantify and examine the compositionof different classesof nonhumic
biomolecules are indicated in Fig. 2.3. Although not indicated in Fig. 2.3, such selective
methodologies can be applied equally to the macroorganic and DOC fractions and to the humic
fractionsto selectivelyremovenonhumicbiomoleculecontamination.
In theclassicalextractionscheme(Fig. 2.3),humic substances aredifferentiatedsimply on the basis
of their extractabilityin alkali solutionat pH valuesrangingfrom 10-13, andsubsequentsolubility on
acidification of the alkali extract of pH 2. The unextractedalkali insoluble fraction is referred to as
humin. The materialwhich remainssolublein the acidifiedalkalineextractis the fulvic acid fraction
while that which precipitatesis the humic acid fraction. All three humic fractionsare not discrete
compounds,with eachfraction containinga multitude of different chemicalstructureswhich can be
further fractionatedand purified. Each fractiontypically containsnonhumictriomoleculesas a result
ofthe nonspecificnatureofthe alkalineextractionprocedure.Purificationofthe humic and fulvic acid
fractions,by removalof the nonhumicbiomolecules,resultsin the isolationof humic and fulvic acids.
The use of alkaline reagents to extract soil organic fractions prior to the application of
characterizationprocedureshasbeencriticizedoflate, especiallywith the developmentoftechniques
which allow thechemicalcompositionof soil organicC to be assessedin situ. Prior to thedevelopment
of such spectroscopictechniques,extractionof soil organicmaterialsfrom the mineral components
was a prerequisiteto their selectivecharacterization. The main criticismsput forward include (l) the
B--50 Soil Chemistrl

Soil 0rgenic Crrbor 0rg8ilc

< 0.43
Removd of dislved organic carbon rtrd mscmrtanic mltler by a'
water ertnctiotr and perticle,rire aod deosity lnctioartion Plent litter, fre and occludcd
\
t crbon, and
rnd cbarrcd rqidqs
F;d

biorolecule ofplent end microbirl

Frrctionrtion on the besisof extrrctrbility in sllqli rnd

."1*,r""".t.tt""i. Carbohydrates HzSOr
Herge
Putoss
t{yd-lJ,"tr.- Uronioscids
Alkrliertrectrble Alkali exiractable A6iDo sugrn
Acid broluble Acid ssluble
Proteinaceous
t i slruclures
HCI AEitro
tcirk
FumFil,tl adal
lFufi:l-c H-".i-iya"..-
I fraction I I fraction I
Removal of norhumic biomolmuls A range of

i i Lignin
residues
CuOoridationrPhoylpropuoid
Tll'{H Eouooenc
lH".t*tdl lTur;;A Thermochemolysis strucluG

A r.ng€ of
550 Dercasing crrbon conteat (g kg-r) 43g fattvrcid
Alipharic o_rycsr9_!9_lyes5
" - srructuG
,t6 Ertncrion
;;;:;;;;.

1.10 510

100 t000

l0 @rooo
Fig. 2.3 Fractionationof soil organic matter basedon chemical and physical properties [Modified from Oades, 1989j

questionable ability of thealkalineextractable

organicmatterto represent thecompositionof thenon-
extracted and whole soil organic fractions, (2) the apparentlack of a relationship between the
brologicalfunctioningoforganic C in soils and its extractabilityin alkalinereagentsbasedon C and
N isotopictracerstudies(Oades,1995),(3) differencesin thechemicalcharacteristics displayedby the
extractedorganic moleculeswhen comparedto those of the samematerialsexisting in soils in an
adsorbedstate(e.g..conformation, cationbindingcapacity,hydrophobicity, etc.),and(4) thecreation
of artifactsduring the extractionprocedure.
Ofgreatest concernis the creationofartifacts during the alkaline extractionprocedure.A receni
study by Zuman and Rupp ( 1995)useddifferentialpulsepolarography(DPP) and spectrophotometry
to examinethe impactof alkalinesolutionson thecleavageof lignin.The rateof lignin cleavageand
releaseof solublearomaticaldehydeswereshownto follow first orderkinetics,with the magnitudeof
the rateconstantdescribinglignin cleavageincreasingexponentiallyover the pH rangeof 7.5 - I 0.5.
Negligible releasewas notedat pH values< 7.5. A similar effect of soiutionpH was notedfor the rate
constantassociatedwith the releaseof aromaticaldehydesdirectly from a sandyloam. The maximum
releaseof aromaticaldehydesoccurredwithin 1 or 2 h for the sandyloam and the lignin, respectively.
Therefore,under the rccommendedconditionsof alkalineextractionof humic materialsfrom soils,
namely, the exposureof soil to a solution of pH l3 for 4 h (Swift, 1996),a significant releaseof
aromatic aldehydes,and potentially of many other aromatic species from lignin may occur.
Acidification of alkalinesolutionscontainingaromaticfragmentsof lignin resultsin an acid-catalyzed
polymerization,and the formation of polymers having chemical structuresand molecular masses
differentfrom thoseof lienin. The releaseof aromaticaldehvdesfrom humic acidsextractedfrom the
Soil Organic Matter B-51

sandyloam usedby Zuman and Rupp (1995)was found to differ from that of the whole soil andlignin
in two ways:(1) releaseof aromaticaldehydeswasinitiatedat pH 3; and(2) thekineticsof releasewere
muchfaster(maximumreleasewasattainedin l0*20 min). The presenceof two differentmechanisms
of releascwas suggestedfrom the polarographicdata. The similar patternsof aromatic aldehyde
releasefrom the whole soil andlignin and thecontrastingpatternnotedfor humic acidssuggestedthat
thepredominantaromaticcomponentsfound in thewhole soil werederivedfrom unalteredlignin and/
or partially degraded lignin fragments,and not from humic acids. This observation,taken in
conjunctionwith thepotentialacid catalyzedpolymerizationof lignin fragmentsextractedby alkaline
reagents,suggeststhat at leasta portion, and potentially a significantcomponent,of the humic acid
fiaction of soil organicmaterialsis not representativeof materialsnaturallypresentin soils,but is an
artifact of the extraction procedure,especiallywhen high pH extractants(pH > l0) are used. In
addition,the cleavedaromaticspecieswhich do not polymerizeon acidificationof the alkalineextract
endup in the fulvic acid fraction,Therefore,someofthe organicspeciesthatend up in the fulvic acid
fractionmay also be a result of the alkalineextractionprocedureemployed.
Swift (1996) suggestedthat the problem of artifact production can be reduced by using mild
extractionreagents(e.g., neutralsodium pyrophosphate);however,the pH of the extractantwould
haveto be decreasedto < 7.5. In doing so,the efficiencyoforganic C extractionwould decreaseto the
point wherethe extractedorganicC would no longerbe an adequaterepresentationof the entire soil
organicC fraction. It is strongly suggestedthat the useof alkalineextractantsbe avoided,and that a
combinationof modernspectroscopic techniquesand/orwet chemicaldegradativeproceduresknown
to be selectivein their action (moleculartechniques)be utilized to characterizesoil organic C.

2.5.1.2 SpectroscopicMethods of Characterization

Modern spectroscopictechniquesthat can be usedto probethe chemicaistructureof soil organicC ln
sirn include solid-staterrC MNR, analyticalpyrolysis,and Fourier transforminfrared spectroscopy
(FTIR). Selected review and researcharticles addressingthe details of the techniques,recent
developments,and their applicationto the study of organicmaterialsin soils are presentedin Table
2.4. Modern spectroscopicmethodsare complementaryand,wherepossible,cfforts shouldbe made
to utilize combinationsof thesemethods to confirm and enhancedata pertaining to the chemical
structureof soil organicmaterials.

Solid-Statet3C Nuclear Magnetic Resonance Spectroscopy(I3C NMR)

Only the appiicationof solid-state']C NMR to soils wili be examinedin this chapter;however,other
forms of NMR includingsolid-state'5NNMR andsolutionstaterrC, rsN,and IP NMR havepotential
appiicationsto the study of organic materialsin soils (seeTable 2.4 for indicative studies).The
greatestpositiveaspectof the applicationof solid-state'rC NMR to soilsandsoil fractionsis its ability
to characterizethechemicalstructureofsoil organicC in sita andnondestructively. A typical spectrum
acquiredby applying the conventionalsolid-statecross-polarization magic anglespinning(CPMAS)
'rC NMR pulse sequenceto soil humusis presentedin Fig. 2.4a(Skjemstadet al., 1997).OrganicC
found in differentchemicalenvironmentscanbedifferentiatedon the basisof chemicalshift (the x axis
in Fig. 2.4aexpressedin units of ppm of the appliedmagneticfield). A review of the solid-staterrC
NMR chemicalshift valuesof organicC found in a wide varietyof known chemicalstructureshasbeen
presented by Duncan(1987).Solid-staterrCNMR spectraacquiredfor mostmineralsoilswith < 50
g C kg-' soil aretypicallydivided into four regionsofchemicalshift becauseofthe largeheterogeneous
mixture of different types of organic C: alkyl C (0-45 ppm), O-alkyl C (45-l l0 ppm), aromaticC
( I 10-165 ppm), and carbonyl C (165-220 ppm). The labelsgiven to eachchemical shift region are
only indicative of the dominant form of organicC present,and therewill undoubtedlybe a rangeof
B-52 Soil Chemistrr

Table 2.4 List of reviewand researcharticlespertainingto the applicationof andrecentdevelopments

in modern
spectroscopic
techniques to the oharacterization
of the chemistryof soil organicmaterials

Title

NuclearMagneticResonance Spectroscopv (NMR)

Applicationsof NMR to soil organicmatteranalysis- historyandprospects(Preston,I 996)
N.M.R. techniquesand applicationsin geochemistry andsoil science(Wilson. 198?)
of soil organicmatterby solid-staterlC NMR spectroscopy
Characterisation (Skjemstader al., 1997)
Nuclearmagneticresonance in agriculture(PfefferandCerasimowicz,1989)
'3CNMR studiesof soilorganicmatterin wholesoils:I. (Kineschet al., 1995)
possibilities
Quantitation
Pvrolvsis-gaschromatograDhv-mass sDectrometrv(PvCCMS)
Characterizationof humic and soil particlesby analyticalpyrolysisand computermodeling(Schultenano
Leinweber.1996)
Thermaldegradation relevantto stlucturalstudies(Bracervellet al., 1989)
of humic substances
Analytical pyrolysisof humic substances and soils: geochemical.agriculturaland ecologicalconsequences
(Schulten.1993)
Pyrolysisandsoft ionizationmassspectrometry
of aquatic/terrestrial andsoils(Schulten,I 98?)
humicsubstances
Infrared spectroscopv(IR)
Characterization andpeatby diffusereflectance
ofhumic acids,composts, Fouriertransfoffninfraredspectroscopl
( N i e m e y e re t a l . , I 9 9 2 )
Vibrational, electronic, and high energy spectroscopic methods for characterising humic substances(Bloom and
l.eenheer, 1989)

structureswithin eachregion,Spectraacquiredfor mineralsoilswith > 50 g C kg-r, peats,forestlitter.

andothermaterialswith high C contentssuchasparticulatesoil organicfractionscanoften be divided
into narrowerchemicalshift regionsindicativeof more discretetypesof C, becauseof higher signal
to noiseratios.
The relative contribution of eachtype of C can be estimatedby expressingthe integralof signal
intensity under a given peak or acrossa given chemical shift region as a proportion of the total
integratedareaof the entire spectrum.Such an approachto assessingthe distribution of chemical
structureswithin a sampleshouldbe consideredas a semiquantitativeanalysisunlessdetailedNMR
experimentsare performed which examine the relative ratesof signal generation(T.") and decay
(T,pH)andtheratesofrelaxation(T,H)foreachtypeofcarbonpresentinthesample(W 1 9i l 8s 7
o ;n ,
Baldocketal.,1989;PfefferandGerasimowicz, 1989;Kineschetal., 1995).Evenwiththecompletion
of suchdetailedexperiments,however,nonquantitativeresultscan be obtainedwhen paramagnetic
materials are presentor where IrC nuclei are separatedfrom rH nuclei. The presenceof paramagnetic
species(metalcationswith unpairedelectronsor organicfreeradicals)candrasticallyreducethe spin-
lattice relaxation time (T,H) such that signals from C in close proximity to such speciesare not
observed.Of principal concernin the applicationof solid-stateNMR to soil is the ratio of organicC
to Fe in the samples(Arshadet al., 1988;Skjemstadet al., 1994).Arshadet al. ( 1988)suggestedthat,
at organicC:Fe ratios> l, adequatespectracan be obtained,but at ratios < l, stepsmust be takento
removethe Fe prior to acquisitionof NMR spectra.Skjemstadet al. (1994) showedthat organicC:Fe
ratios> I do not necessarilyindicatethat reasonablespectracan be accumulatedif sampleshavehigh
magneticsusceptibilities,andthat therelativevisibilily (RV) (integratedspectralareag-r organicC in
the sample)of soil organicC could be estimatedby Equation[2.5], where OC/Fe is the ratio of the
gravimetric percentagesof organic C to that of Fe in the sample.RIF is the remaining inorganic
Soil Organic Matter B-53

H
- Y_ot
?- H
-o,-l
l, {a)
H-9-oH H -N<
,z-l H

/;

a
tll#
d)
a

o (b)
8 8 0 2d
E
5 6 0

, . ] l
.,]ill,,lr
,rll
,'r II
> 4 0
E
o

100 150 300 350

(c,

I
I
0

3500 3000 2500 2000 1500

Wavelength (cm-l)
Fig,2.4 Examplesof data obtainedusing modern spectroscopictechniquesto study the chemicalstructureof soil
organic matter. a) Solid-stateIrC NMR spectrumof soil humus showing four generalchemical shift regions and
typical chemical shift assignments(modified from Skjemstadet al., 1997).b) Pyrolysis-fieldionization mass spec-
trum of a humic acid (Schulten,1987).c) Diffuse reflectanceFourier transforminfrared spectrumacquiredfor the
-C
0-2.5 cm layer of a mineral soil (52 g C kg-') by subtractionof the spectrumobtainedfor a sampleheatedat 350
from that of the unheatedwhole soil.

fraction expressed as a gravimetric percentage of the total mass of the sample after HF treatment, and
listhemassmagneticsusceptibility(pmtkg').Repeatedpretreatmentofsoilswitba2ToHFsolution
reduced Fe concentrations and concentrated organic C through the dissolution of a portion of the
inorganic matrix, thus enhancing the NMR visibility of the organic C in soil samples considerably. The
use of such pretreatments must be examined carefully, since the HF pretreatment may remove
significant quantities of organic C.
B-54 Soil Chemistr!'

RV = 5.33+ 0.375(OCiFe- 0.14"1

RIF + 0.0431-r) f1 <t
L'.J 1

The issueof the proximity of r3Cto rH nuclei arisesbecauseof the use of cross-polarizationin
solid-staterrC NMR analyses.Cross-polarizationcan be usedto enhancesignalintensity by a factor
of 4 under optimum conditions,but organicC that is separatedfrom hydrogenby > 5 bond lengths
cannotcross-polarizeand will not be observed(Snapeet al., I 989). OrganicC in soils which contain
appreciablecontentsof highly carbonizedorganicmaterialssuchas charcoal,charredplant material
and coal will not be detectedquantitativelyusing the conventionalCPMAS analysis,and a Bloch
decaypulsesequencemust be used.Use ofthe Bloch decaypulsesequenceis restrictedbecauseofthe
exceedinglylong accumulationtimesrequiredto obtainspectrawith reasonablesignal-to-noiseratios.
Additional chemicalinformationon soil organicC can be obtainedthroughthe use of interrupted
decoupling (ID), proton spin relaxation editing (PSRE), and mixing of proton spins (MOPS),
techniques.The ID pulsesequence(OpellaandFrey, 1979),alsoknown asthedipolardephasingpulse
sequence,is capable of differentiating immobile protonatedC from nonprotonatedC or mobile
protonatedC. It hasbeenusedto assessthe proportionof protonatedversusnonprotonatedaromatic
C (Hatcher,1987),to differentiatebetweenmethoxyl and N-alkyl C in the 45-60 ppm chemicalshift
r e g i o n ( H a t c h e1r ,9 8 7 ) , a n d t o e x a m i n e t h e n a t u rtehoefs o i l a l k y l C f r a c t i o n ( B a l d o c k e t a1l .9, 9 0 a , b ;
Kdgel-Knabneret al., l992a,b). PSRE utilizes differencesin T,H values within a solid sampleto
derivesubspectra associated with fastandslow relaxinghydrogen (NewmanandHemmingson,1990).
The presenceof diff'erentT,H valueswithin a singlesampleimplies a spatialseparationof organic
materialsassociatedwith eachsubspectrumon a scaleof > 30 nm. Resultsfrom PSREanalyseshave
demonstrateda spatialseparationof polymethylenefrom aromaticandcarbohydrateC in HF-treated
humin (Prestonand Newman, 1992),plant residueC from humified C (Golchin et al.,1997a,b),and
charcoal-likeC from humified C (Tate et al., 1990; Golchin et al., 1997b).MOPS representsan
extensionof the PSRE techniqueto include differentiationof C on the basisof both T,H and T,pH,
which provides information pertainingto the chemistry of C separatedby > 30 nm and 2-30 nm,
respectively.In applyingthe MOPS techniqueto wood,Newman(1992)was ableto demonstratethat
cellulose microfibrils with a diameter of approximately 14 nm were surrounded by a lignin
hemicellulose mixture.

Analytical Pyrolysis
Analytical pyrolysisrefersto thecharacterization
of amaterialby instrumentalanalysisof its pyrolysis
products and encompassesa group of methodologiesincluding offline pyrolysis, pyrolysis-mass
spectrometry,derivatizationpyrolysis-massspectrometry,and pyrolysis-gaschromatography/mass
spectrometry.A detaileddescriptionof thesetechniquesis presentedby Schultenand Leinweber
( l 9e6).
Application of thermalenergyto organicmaterialsresultsin a cieavageof the weakerbondsin the
organicmoleculespresent,and a releaseof a rangeof reactionproducts.The thermalenergycan be
applied using two techniques:quasi-instantaneous heating (Curie point pyrolysis) or a controlled
temperatureprogrammedheating.Temperatureprogrammedmethodshave beencriticized becauseof
the potential to form secondaryreactionproductsunrelatedto the organic materialspresentin the
sample.Curie point pyrolysis methodsarerapid, sensitive,highly reproducibleand can be appliedto
small samples.
In offline pyrolysis, the loss of C andTorN from a sampleduring pyrolysis is measuredwith no
attemptto characterizethe chemicalnatureof the pyrolysis products.Using a set of 64 soil samples
with organicC contentsrangingfrom I to 460 g kg-t, SchultenandLeinweber(1996)showedthat the
amount of volatilization was proportionalto the soil organicC content.It was also shown that the
Soil Organic Matter B-55

proportionsof organicN which volatilized were often greaterthan thoseof organicC. In pyrolysis-
massspectrometry(Py-MS), the pyrolysis reactionproductspassdirectly into a massspectrometer
that is capableof separatingthe productson the basis of m,/zvalues (masslchargeratios). Several
methodsof ionization are availableto promote the movementof reactionproductsthroughthe mass
spectrometer:field ionization(FI), chemicalionization(CI), fastatombombardment(FAB), andlaser
ionization (LI). lrrespectiveof the method of ionization utilized, distinctive patternsof pyrolysis
products,often referredto as fingerprints,are produced(Fig.2.ab). Signalslocatedat various m/z
valueswithin thesefingerprintscanbeconsidereddiagnosticforparticulartypesof organicmolecules.
For exampie,basedon the work of Schultenet al. (1987),Schnitzer(1990) tentativelyidentified
severalof thesignalsin Fig. 2.4basfollows:polysaccharides (m/z valuesof 60. 82,96,110,and 126),
heterocyclicN-containingstructures(mlz valuesof 79,92, and 117),and lignin (m./zvaluesof 212,
302,344). After normalizationof the m/z peak intensities,a qualitativeassessment of changesin the
chcmical natureof the organicC in samplesof whole soils or soil fractionscan be determined.For
example,differencesin the chemicalcompositionof organic C containedin particle size fractions
isolatedfrom two mineral soils werepresentedby Baldock et al. ( 1991).Lists of otherapplicationsof
Py-MS and the appropriatereferencesare presentedby Schnitzer(1990) and Stevenson(1994).
A cautionarynoteregardingthe comparisonof differentof m/z signalintensitiesis required.First,
the intensitiesobservedat any singlemlz valuemay resultfrom multiple pyrolysatefragmentsif they
havethe samemass:chargeratio. Second,the volatilizationof different typesof pyrolysis fragments
varies(e.g.,in Py-FIMS volatilizationdecreases with increasingpolarity of thefragments).As aresult,
differencesin signal intensitiesat variousm./zvalueswithin any one soil sampledo not necessarily
correlate with contents of the parent moleculespresentrn the original sample. It is appropriate,
however,to utilize variationsin a given mlz signalintensityto infer differencein structuralchemistry
acrossa seriesof soil samplesrun undera constantset of analyticalconditions.
Various on- and offline derivatizationprocesseshavebeendevelopedto reducedifferencesin the
volatilization of the various pyrolysis products. Derivatization Py-MS techniques utilizing
tetramethylammoniumhydroxide (TMAH) convert hydroxyl and carboxyl groups into their
equivalentmethyl ethersand methyl esters,respectively.Pyrolysismethylationwith TMAH enabled
detectionof aliphaticCr-C, monocarboxylicacid methyl esters,C,,-Crodicarboxylic acid dimethyl
esters,benzenecarboxylicacid methyl estersand a rangeof other methylatedcompounds(Schulten
andLeinweber, 1996)The incorporationof a gaschromatographbetweenthe pyrolysis chamberand
themassspectrometercanfurtheraid in theseparationof similar pyrolysisfragmentsprior to detection
and analysisby the masssp€ctrometer.

F aurie r Tran sfor m I nfrar ed Spectro sc opy F f I R)

In its application to studiesof the chemical structureof soil organic C, the absorptionof infrared
radiationof different frequenciescan be usedto determinethe type of the atornsto which C is bound
as well as the natureof the bond. Detailed identificationof chemical structureis possiblefor pure
sirnpleorganicmolecules,but the dominanceof signalsderivedfrom mineral componentslimits the
applicationof FTIR spectroscopyto the studyof soil organicC in mineral soils.Even afterextracrion
of organic materialsfrom soils, the complex and heterogeneous nature of the organic C results in
spectraexhibiting absorptionbandsspanningwide rangesoffrequencywith few well-resolvedpeaks.
However, comparisons of spectra obtained before and after various chemical degradation or
derivationtreatments(e.g.,carbohydratehydrolysisand methylationor acetylation)can yield useful
information.The useof differencespectra(spectrumof an untreatedsampleminusthat of a pretreated
sample) can provide insight into chemical structures.An example of the difference spectrum
associatedwith the removal of organicC from a soil is given in Fig2.4c and can be usedto provide
B-56 Soil Chemistry

an approximation of the chemical nature of the organic materialsremoved in the pretreatment,

provided that a significant alterationof the soil mineral componentshasnot occurred.
Infrared spectra contain a vasl amount of information pertaining to chemical structure.The
problem experiencedto date has been how to get at the information and utilize it in a meaningful
manner.The useof multivariatestatisticssuchas partialleastsquares(PLS) allows thoseportionsof
an FTIR spectrum that are correlatedto other measurements(e.g., total sugar concentrationas
identified by HrSOohydrolysisand subsequentcolorimetricdetermination)to be identified acrossa
rangeof soil sampies.Once such relationshipshave been identified,the contentof the required
parameterof interestcan be estimatedwith a known degreeof precisionusing FTIR in conjunction
with the predictive equations.The rapid natureof modern infrared analyses(severalmin./sample)
when utilized in this manner,would facilitate the acquisitionof data without the needfor utilizing
laboriousroutineprocedures. Skjemstadetal. (1997)havepresented theresultsofsuch an evaluation
in which a strongcorrelation(r2=A.917'lwas found betwcenaromaticC contentasmeasuredby solid-
stateCPMAS 'rC NMR and that generatedusing PLS proceduresin conjunctionwith FTIR. Given
that the typical time requiredto acquirea solid-staterrc NMR spectrumfor a mineral soil is 6-24 h,
an enonnouspotentialexiststo utilize FTIR datato facilitatean assessment of the chemicalnatureof
soil organic C, provided that enough '3C NMR data exists to complete an appropriatecalibration
procedure.

2.5.2 Dissolved Organic Carbon

Dissolved organic C (DOC) is a small but important and dynamic fraction of soil organic C. Its
importancerelateslargely to its mobiiity, both within the soil and from the soil into groundwateror
surfacewater bodies.From a biological point of view, it providesa mobile sourceof energyand the
nutrientsassociatedwith it can make an importantcontributionto nutrient availability and cycling.
From a chemicalpoint of view it behavesas a reactivecomponentof the soil solution,and facililates
transportof othermaterials.A detailedreview of informationon DOC in soilswasrecentlycompleted
by Herbertand Bertsch(1995).
The term dissolved refers to materialsin solution that do not settle out under the influence of
gravity. The smallerand more polar an organicmolecule,the more likely that it will stay in aqueous
solution.Whetheror not a particularorganicmoleculeis dissolveddependson the watercontentof the
soil, and the natureof the surfacesand other solutes.At the larger,lesspolar end of the range,the
boundaries between dissolved, colloidal and particulate organic matter are not definite. The
definitionsareusualiymadeoperationally.Forexample,DOC is usuallydefinedasorganicC thathas
passedthrougha particularsuctioncup or filter or that occursin the supernatantafter centrifuginga
soil suspensionat a given relativecentrifugalforce for a given period.Theseoperationalparamcters
should be clearly statedin discussionsof DOC in soil, and it is importantto note that processessuch
as adsorptiononto or clogging of filters or suction cups may significantly influence the natureand
amountof materialobtained(Grossmanand Udluft, I 99 I ). In this chapter,DOC hasbeendefinedas
that which passesthrougha 0.45 pm filter.

2.5.2.1 Isolation and Measurement

Before measurementor characterization,DOC must be extractedfrom the soil. The means of
extractiondeterminethe amount and natureof the materialextracted(Herbert and Bertsch, 1995).
While extractionat or near the water contentof interestis desirable,such a proceduremay resuit in
very small volumesbeingcollected.At high soil waterpotential(morenegativeanddrier), extraction
becomesimpractical, but at low soil water potential (less negativeand near saturation),sufficient
volumesareoften easily obtained.In the field, DOC hasbeenextractedby the useof tensionor zero-
Soil Orpanic Matter B-57

tensionporouscupsor plates,or by wick lysimeters(Grossmanand Udluft, 1991).In the laboratory,

DOC can be extractedby forcing solutionout of the soil througha porousmembraneusingvacuumor
centrifugalforceorbyleachingrepackedcolumnsorundisturbedcores(Dunnivantetal.,1992).For
convenience,many studieshaveusedextractsmadeby shakingsoil with wateror dilute saltsolutions,
followed by separationof the soiutionby centrifugationor filtration. Material extractedby alkaline
soiutionshas also beenusedto representDOC. However, this practiceis likely to be inappropriate,
becausematerialsdissolvedby alkali differ from thosefound dissolvedin soil solution (Novak and
Bertsch,1991).
Once a soil extract has been obtained,DOC contentsare estimatedby oxidizing the dissolved
organicC to CO, and thenmeasuringthe amountof CO?producedor oxidantconsumed.A common
techniquethat appearssatisfactoryin mostcasesis oxidationby persulfateand UV radiationfollowed
by detectionof the CO, evolved by IR absorbanceor other techniques.Techniquesthat measurethe
amountof oxidant consumedfacesimilar problemsas thosediscussedin Section2.3 for the analysis
of soil organicC contents.The yellow to brown color of DOC hasresultedin the use of absorbance
in the visible or UV rangeto quantify DOC concentrations. Absorbanceis simpleand convenientand
readily lends itself to continualmonitoring and logging. However,it shouldbe kept in mind that it is
not a direct measureof concentration,as different organicmaterialsdiffer widely in their absorption
properties.

2.5.2.2 Gains, Lossesand Amounts

DOC entersthe soil asleachatefrom vegetationand litter, and is generatedwithin the soil throughthe
processesof excretionfrom organismsand desorptionor dissolutionfrom the solid phase.It is lost
through biological uptake,extracellularmineralization,sorption,precipitationand as leachateinto
surfacewater coursesor groundwater.The concentrationof DOC is governedby all theseprocesses,
and typically rangesfrom 5-50 mg L-' in surfaceand litter horizons,andfrom 0.5-5 mg L-' or lessin
B and C horizons(McDowell andLikens, 1988).
Plantroots and microorganismsexcretea largevariety of solubleorganicmateriais.For example,
in anaerobicsoils, organic acids(mostly low molecularweight fatty acids)are major byproductsof
decomposition.Uptake of organic molecules by roots has been documented,but this removal
mechanismis probablyof minor importance.
Microbial uptake,decomposition,and mineralizationare Lhemajor mechanismsdeterminingthe
concentrationand natureof DOC. The amountof DOC in soil hasbeencorrelatedwith soil respiration
and denitrificationpotential(Burford and Bremner,1975;Davidsonet al., 1987).From this, it is
sometimesinferred that DOC is the active fraction of SOM, or that it is the pool turning over most
rapidly. However,equatingDOC with the activepool is only a very rough approximation.Although
many organicsubstrates(e.g.,cellulose)are solubilizedby enzymesprior to mineralization,the flux
of readily mineralizedsubstratesthroughthe DOC pool is not necessarilyreflectedin the size of the
pool, becausethe concentrationof readily available materials such as monosaccharides,simple
organic acids, or amino acids is kept very low due to their rapid assimilationor mineralization.
Nevertheless, the concentrationof readilymineralizableDOC may be temporarilyhigherin some
situations,suchas whererootsareactiveor wherefreshorganicresidueshavebeenadded(Nelsonet
al., 1994).The proportionof DOC thatis mineralizedin short-termincubationstudiesgenerallyvaries
between3 and40% (Boyerand Groffman,1996;Nelsonet al., 1994).and varieswith the soil depth
from which it was extracted(Nelson et al., 1994).DOC, as a whole, may not be any more easily
mineralizedthan particulateor adsorbedfractions.SomeDOC appearsto be biologically recalcitrant
(ZsolnayandSteindl,l99l ), with thereasonsnot beingwell understood. While physicalentrainment
B-58 Soil Chemistry

may protect particulate organic malter from microbial attack. it is doubtful as a stabilization
mechanismfor DOC which candiffusetowardsorganisms(Adu and Oades,1978).
The processesof adsorption/desorption and dissolution/precipitationare governedby the nature
and concentrationof the DOC and other solutes,pH, and the natureof the solid phasematerials.
Sorptionoccurson many soil materialsthrougha varietyof mechanisms(Oades,1989).It is greatest
at low pH (Jardineet al., 1989), and large or hydrophobic moleculesare preferentiallyadsorbed
c o m p a r e d t o s m aol lr h y d r o p h i l i c m o l e c u l e s ( D u n n i v a n t e t a l . , 1 9 9 2 ; K a i s e r1e9t a9l6. ,)I.n s o i l s w i t h
high surfaceareaor high clay content,concentrationsofDOC are kept low by adsorptionoforganic
moleculesontomineralsurfaces(Nelsonet al., 1993).Wheremultivalentcations,suchasFe or Al in
acid soilsandCa in neutralto alkalinesoils,areabundantDOC concentrations arekept low because
organiccomplexesof multivalentcationsdo notionizereadilyandareof relativelylow solubility.Ong
andBisquc ( 1968)showedthat theflocculatingeffectof cationson DOC wasproportionalto the sixth
power of their valence.Multivalent cationsmay also form bridgesbetweendissolvedorganic
moleculesand mineral particles,therebytaking the organic moleculesout of solution (Nelson and
Oades,1998).In water-saturated sediments,DOC concentrations can be high due to dissolutionof Fe
and Al complexes(Thurman,1985),and this is prohablyalsothe casein waterloggedsoils.In soils
with low surfaceareaor in soilswith a high proportionof monovalentcations,a higherproportionot
organicC tendsto be dissolved(Nelsonand Oades,1998).Seasonalfactorssuchas temperatureand
moistureand managementfactorssuch as acidification,tillage and applicationof fertilizer, lime, or
manureall influencetheamountandnatureof DOC in soils(HerbertandBertsch,1995).In a leaching
cnvironment,DOC that is not retainedin the soil by adsorptionor precipitationmechanismsis lost to
groundwateror surfacewater (Nelson et al., i993), where it has a significant influence on water
chemistrv.Preferentialflow throughmacroporescan greatly enhancetransportthrough the soil and
lossto waterbodies(Jardineet al., 1990).

2.5.2.3 ChemicalStructure
The chemical structureof soil DOC is complex and varied. Molecular weight rangesfrom a feu
hundredto lrundredsof thousands(HomannandGrigal, 1992).Conventionalwet chemicalmolecular
techniquescan typically identify about507oof the structuresin DOC; the restremainsunidentifiable.
Easily identified structuresinclude carbohydrates,hydrocarbons,polyphenolic compounds,and
amino, aiiphaticand aromaticacids(Stevenson,i994). Complex materialthat is not easily identified
is commonly referredto as humic substances, most of which can be classifiedas fulvic acid because
it remainsdissolvedat iow pH.
Due to the complexity of DOC, samplesarefrequentlyfractionated,either asa characterizationor
preparativetechniquefor other characterizationmethods.One of the most widely usedfractionation
techniquesinvolvessorptionon nonionicand ion exchangeresins(Herbertand Bertsch,1995).These
and reiatedtechniquesyield fractionstermedhydrophilicand hydrophobicacids,basesand neutrals
DOC hasalsobeenfiactionatedon the basisof molecularsize,usinggel permeationchromatographr
or ultrafiltration (Herbertand Bertsch,1995).Materialsin DOC fractionsare still complex,and it is
not alwaysclear to what extentmaterialsare lost, gainedor alteredduring the fractionationprocess.
Important characteristicsof DOC include its acidity, chemicalstructure,and sorption behavior.
Titratabieacidity, largely due to low molecularweight organicacids,variesfrom 6 to l5 mol. kg-' C
(Herbert et al., 1993). Examination by 'tC NMR spectroscopyhas shown that DOC consistsof
carbohydrate,aromatic,aliphatic and carbonyl structures(Novak and Bertsch, 199l). In litter and
surface horizons, DOC contains a high proportion of aliphatic material and hydrophobic acids.
whereas,in deeperhorizons,it is lessaliphaticand dominatedby hydrophilic acids(Easthouseet al..
1992\.
Soil Organic Matter B-59

2.5.3 ParticulateOrganic Matter

Particulateorganic C (POC) is defined as the C found in fragments or organic debris with a
recognizablecellular structure.POC may be derived from any source,but is usually dominatedby
piecesof plant structures.in the following discussion,POC found in Histosolsandon the mineralsoil
surface(litter) will be dealt with separatelyfrom that found within the mineralmatrix.

2.5.3.1 POC in Histosols and Forest Litter Layers

Histosolsandforestlitter layerspresenta simplesystemin which to characterize thechemistryof POC
and the chemical changesassociatedwith POC decomposition.The absenceof mineral particles
iacilitatesa selectivechemicalcharacterizationof POC, and reducesthe biological stabilizationof
iabileorganicC via adsorptiononto mineral surfacesor physicalentrapmentwithin aggregationsof
mineral particles.In these highly organic materials,decompositionand chemical transformation
processesare controlled by the compositionof the plant residuesand the changesimparted by the
decomposer community.
The chemicalcompositionof organicC containedin Histosolshas beenexaminedby numerous
researchersusing r3CNMR. Using rubbed fiber (seeLdvesqueet al., 1980 for a definition) as an
indicatorof extentof decomposition,positivecorrelationswereobtainedwith thecontentsof alkyl and
aromaticC and negativecorrelationswere obtainedwith the contentsof O-alkyl C (Hammondet al.,
1985).CultivatingHistosolsurfacelayersinducedan increasein alkyl C andreductionsin O-alkyl and
aromaticC, relative to the uncultivatedHistosol (Prestonet al., 1987).The reductionin aromaticC
presumablyresultedfrom the presenceof a more oxidizing environmentin the cultivatedsoil, and an
enhancedactivity of aerobiclignin degradingfungi. Prestonet al. (1989b) and Norddn et al. (1992)
examinedthe chemical changesassociatedwith decompositionof peat by performing r3CNMR
analyseson particle size fractions.Nord6n et al. (1992) observeda progressiveloss of identifiable
plantstructuresandan accumulationof alkyl C andlossof O-alkyl C asparticlesizedecreased. Similar
resultswere obtainedby Prestonet al. (1989b), but a ioss of aromaticC was also noted, and the
magnitudeof the chemicalchangesobservedacrosstheparticlesize fractionsincreasedasthe overall
extentof decompositionexhibitedby the Histosolsincreased.
Assessmentsof the chemicalchangesinducedby decompositionin forestsoils typically includea
characterization ofthe different litter layersencounteredin progressingfrom the fresh litter locatedat
thetop of the forestfloorthrough to the well-humifiedmaterialslocatedat the top of the uppermineral
soil horizon. '3C NMR datacollectedfor a rangeof German forestsoils exhibiting examplesof the
mull, moder,andmor humusforms showedan increasein alkyl C anda decreasein O-alkyl C contents
with depth for all soils (Zech et al., 1992).Changesin aromaticC contentwerelessconsistent,but in
general,they tended to decreasewith increasingextent of decomposition.Baldock and Hatcher
(unpublisheddata,seeBaldocketal., 1997)observedasimilarpatternofalkylandO-alkylCcontents
in litter layers found under red pine and tamarackplantations,but aromatic C content tended to
increasewith extentof decomposition.Variationsin the aromaticC contentwith increasingextentof
decompositioncontentaresuspected to arisefrom differencesin theactivity of lignin degradingfungi.
An assessment of the possiblemechanismsaccountingfor an accumulationof alkyl C in forestlitter
layersis presentedin Section2.5.4,2.
In studies where depth profiles are used to assessthe chemical changes associatedwith
decomposition,it is assumedthat the compositionof the original plant residuesdepositedon the soil
surfacehas not changedas the litter layers have developed.Where significant differencesin the
vegetativesourceof organicC exist, variationsin the chemicalcompositionof litter and humified
organicC are possible.Krosshavnet al. (1992) observeddifferencesin the chemicalcompositionof
organic C found in peatsand forest litters derived from different types of vegetation.For samples
B-60 Soil Chemistry

exhibiting a similar degree of decompositionand organic C content, the greatestdifferencesin

chemicalcompositionwere notedbetweenpeatand forestorganicC; however,differencesbetween
foresttypcswerealso noted.Thus.whencharacterizingthechangesin chemicalcompositioninduced
by decompositionin different depositsof terrestrialorganic C, care must be taken to ensurethat
differencesin vegetativeback_eroundare not confoundedin the analysis.

2.5.3.2 Particulate Organic Materials Found Within the Mineral Soil Matrix
POC found within mineral soilsis usuallydominatedby plant-derivedmaterials,but can alsocontarn
fungal hyphae, spores. pollen grains, and faunal skeletons, as demonstratedby microscopic
examinations(Watersand Oades,1991;Oadcsand Waters,1991).This fractionof soil organicC
servesas a sourceof both energyand nutrientsfor soil organisms,and as a sourceof nutrientsfor
plants.POC fills an intermediatepositionbetweenfreshundecomposed plant materialsand the more
decomposedhumusfraction.POC hasbeenseparatedfrom the mineralmatrix by two main methods:
(l) sievingof dispersedsoil samplesto yield amacroorganic fraction,and(2)collectionof dispersed
soil materials*'hich float on a heavy liquid to yield a light fraction (Gregorichand Janzen,1996).A
discussionof the methodologiesusedto separatethe macroorganicand light fractionsfrom soil is
given in Gregorichand Ellert ( 1993).Although both POC fractionsaredominatedby plant residues,
the natureof the materialscollectedin eachfractionmay differ. In fractionscollectedon the basisof
particlesize.humified organicmaterialsboundstronglyto Iargeinorganicparticlesandorganicdebris
coatedwith mineralparticleswill be retainedon the sievesand includedin the macroorganicfraction.
In the light fractions,such organo-mineralcomplexesmay have a density higher than that of the
fractionatingsolution and will not be includedin the light fraction.
A prerequisitefor the collectionofeither type of POC fractionis a dispersionofthe soil, preferably
usingphysicalprocesses which minimizealterationsto the chemicalcompositionand particlesize
distributionof organicfragments.Ultrasonicdispersionis now utilizedwidely to accomplishthis task;
despite the potential for a fragmentationof the organic particles and a redistribution of organrc
materialswithin the soil with this method(Elliott and Cambardella,1991;Cambardellaand Elliott,
1993). The amount of organic C which accumulatesin the macroorganicand light fractions is a
function of the intensityof dispersionand the naturecf thedispersingmedium.Golchin etaI. (1994a)
observeda loss of ltght fraction C (< 1.6 Mg m ') with increasingdurationof ultrasonicdispersion,
when the dispersionwas accomplishedin water.The procedurewhich maximizedthe extractionof
light fractionC involved an initial removalof a free light fraction by gentleend-over-endshakingof
soil in the heavy liquid, followed by an extraction of the POC occluded within mineral particle
associationsby using a 300 s ultrasonictreatmentin the heavyliquid.
The lower size iimit of the macroorganicfraction varies between investigations,but usually
correspondsto thelower sizelimit of the sandfraction,20pm for theISSSand50pm for theAmerican
particle size classificationsystems.Solid-stater3CNMR was usedby Oadeset al. (1987, 1988)and
Baldock et al. ( 1992)to determinethe chemicalcompositionof the organicmaterialsassociatedwith
various particle size fractions after ultrasonic dispersion and fractionation by sieving and
sedimentation.A density separationwas applied to the macroorganicfractions to concentratethe
organic C and allow acquisitionof acceptable'3C NMR spectra.The chemical compositionof the
largestmacroorganicparticles(250-2000 pm or 53-2000 pm) resembledthat of plant materials.The
reduction of macroorganicparticle size to 20-53 pm, induced via an increasein the extent of
decomposition,was associatedwith a lossof O-alkyl C and an accumulationof aromaticand alkyl C.
Similar results were obtainedby Skjemstadet al. (1993) for four additional Australian soils. The
changesin chemicalcompositionnoted by Baldock et al. ( 1992)were consistentwith a preferential
utilizationof carbohydratestructuresby soil microorganismsanda preservationof lignin andaliphatic
Soil Organic Matter B-6r

structuresduring decomposition.In progressinginto the finer fractions,wherethe dominantform of

organic C would be microbial metabolic products and humified materialsadsorbedonto mineral
surfaces,aromaticC contentsdecreasedand alkyl C contentsincreasedsignificantly.The increased
alkyl C contentcould not be explainedby a selectivepreservationofplant-derivedalkyl C alone,and
it was postulatedthat a contribution was made from microbial alkyl C synthesizedas a metabolic
productof decompositionprocesses. Theseobservationsled to thedevelopmentof a simplified model
which describestheoxidativedecompositionof POC fragmentsin mineralsoils(Baldocket al., 1992).
The model is consistentwith a biopolymerdegradationmodelproposedby Hatcherand Spiker( 1988)
for the genesisof humic substances.
The separationof light fractions from soils utilizes the difference in particle density between
organicand mineralparticles.Organicparticlesgeneraliyhavea densityof S L0 Mg mr while that of
mineralparticlesis > 2.0 Mg m-t. Most studies,where light fractionshavebeenisolated,have used
heavyliquid densities rangingfrom 1.5- 2.0Mg m-r;however,liquidswith densitiesaslow as 1.0Mg
m-r havebeenusedfor the isolationof light fractionsfrom soilshaving a iow mineralparticledensity,
suchas Andisols(Golchinet ai., 1997b).Studieson soil aggregation havesuggested that many soil
aggregates havecoresof organicparticles(Watersand Oades,199I ) and that macroaggregates form
aroundparticlesofplant residues(Beareet aL.,1994a; Buyanovskyet at.,1994;Golchinet al., 1998).
As a result,two forms of light fractionPOC exist in soils:( I ) freePOC without significantassociation
rvith mineral particles,and (2) occiudedPOC strongly associatedwith mineral particlesor buried
rvithinsoil aggregates. The extentto which a soil is disruptedwill, therefore,dictatethearnountof free
and occluded light fraction releasedand measured,particularly in highly aggregatedfine-textured
soils.The chemicalcompositionof free and occludedlight fractronswas examinedby '3CNMR for
iive different soil types (Golchin et al., 1994a).Relative to the free light fractions, which had a
chemicalcompositionsimilar to that of the plant materialsdepositedon the soil, the occludedlight
iraction always showed decreasedcontents of O-alkyl C and increasedcontents of alkyl C. A
'ignificant increasein aromaticC wasobservedfor two of thefive soilswhenprogressingfrom the free
to occludedlight fractionsandonly minor changesin the carbonylC regionweredetected.This result
rndicatedthat the free and occluded POM in soils are chemically distinct, and that the occluded
fractionexhibits a chemicalstructureconsistentwith a more highly decomposedPOC fraction.This
*'ork was extendedto examinethe natureof the organicmaterialsassociatedwith the occludedlight
tractionin more detailby fractionatingit into four densityclasses: < 1.6,1.6-l.8, 1.8-2.0,and> 2.0
Mg - t (Golchin et al., 1994b).Again, different chemical compositions were observedfor the
differentciassesof occludedorganicC. Progressing from the 1.8-2-0to 1.6-1.8to < 1.6 Mg m-'
occluded fractions, chemical changes were again consistent with an enhanced extent of
decomposition.Microscopicexaminationof theseoccludedfractionsindicatedthat the< 1.6 and 1 6-
I 8 Mg m-r fractionsexistedas fragmentsof plant debrisexhibiting characteristicsassociatedwith
e\tensivedecomposition(e.g.,the presenceof lignin coils and large pores).The 1.8-2.0Mg rn-:
fractionwasfoundto existasonly slightlydecomposed plantfragmentsstronglyboundto andburied
w'ithina mineralmatrix.The chemicalcompositionof organicC containedin the> 2.0Mg m-3fraction
did not resemblethat of plant fragments,and wasconsideredrepresentative of microbial residuesand
humified organic materials of piant origin adsorbedonto mineral surfaces.These results were
summarizedby Golchin et al. ( 1994b)in amodel linking thechemicalcompositionof the light fraction
POCto decompositionandaggregation.The modelwas supportedby subsequent work examiningthe
or*canicC turnoverratesfor the variousfree and occludedPOC light fractions(Golchin et al., 1995)
andthenwas extendedby Golchinet al. (1998)
in addition to the contributionsof deconposedplant residuesto soil POC fractions,evidenceof
sisnificantcontributionsto POC fractionsfrom charcoalor charredresiduesin somesoils has been
u-otr SoilChemistry

presented(Skjemstadet al., 1996b;.After treatingsoil silt fractions(< 53 gtm)with an ultraviolet

photo-oxidatit'rn processcapableof oxidizingmost of the biologicallyderivedorganiccomponents
found in soils (for a descriptionof the method, see Skjemstadet al., 1993),the residual organic
materialstrf threesoilsshoweda particulatemorphologyanda chemicaicompositionconsistentwith
charcoal."fhe lalge broadaromaticC peak observedin '3CNMR spectraacquiredfor the ultraviolet
photo-oridiz-edand HF-treatedsampleswas similar to that found for chars produced by heatrng
celluloseto > 400 "C (Shafizadeh, 1984),andfor thermallydegraded cork (PascoalNeto et al., 1995).
The sisnrficantenhancements notedin thearomaticregionof r3CNMR spectraacquiredusinga Bloch
decavpulsesequence,relativeto the standardcross-polarization pulsescquence,were alsoconsistent
ri ith the highly condensed/nonprotonated aromaticC typically found in charcoaland charredplant
residues. Skjemstadet al. ( 1996)calculatedcharcoalC contentsof 3.2,3.4,and8.3mg charcoalC g-'
-<oilrvhichaccountedfor up to approximately307cof the total organicC found in the soils. Golchin
r't al. ( l997a,b)examinedthe natureof the POM fractionin a seriesof Andisois,in which the length
ol titne sinceannualburningofgrasslandhadceased,differed.UV photo-oxidationwas unsuccessful
rn identifying a residualcharcoalcomponentwithin the POC fractions becauseof the presenceof
rnorganiccementingagentswhich are not removedby the photo-oxidationprocedure.However,data
acquiredfrom the PSRE and Bloch decayNMR techniquesindicatedthat,relative to the site where
annualburninghad not beenpracticed,annualburningof grassesled to thepresenceofa charcoal-like
fraction as evidencedby the following characteristics:(l) nonlignin highly aromatic C separated
physically from undecomposedplant residuelike C and (2) the presenceof condensedand proton
deficientaromaticC (Golchin, 1997a).Subsequentdensityfractionationof theseAndisols,followed
by applicationof PSRE and Bloch decayNMR experiments(Golchinet al., 1997b),showedthat
charcoalwas distributedthroughoutthe 1.0-2.0 Mg m-t fractions.However,the charcoalaccounted
for a greaterproportion of the organicC in the < L6 and 1.6- 1.8 Mg m-t occludedPOC fractionsof
all sites,eventhosewithout a recenthistoryof burning.
The presence of significant quantities of nonlabile charcoal in soils will have significant
implications for studiesof POC compositionand dynamics.The aromaticportion of soil fractions,
afteraccountingfor Iignin andlignin like structures(e.g.,tannins),is typically consideredto be derived
from humic substances.Using estimatesof lignin and tannin contentsbased on 'rC NMR data,
Skjemstadet al. (1996) demonstratedthat much, if not all, of the aromatic C remaining, after
accountingfor lignin and tannin structures,could be accountedfor by their estimatesof charcoalC,
and that extractedhumic acid fractionshad chemicalst"ructures consistentwith charcoal.Models of
POC dynamicstypically utilize total organicC measurements to quantify the size of POC pools.The
presenceof even small quantities of inert charcoal C in POC fractions could significantly alter
estimatesof turnovertimes and radiocarbonagesassociatedwith the fractionof soil POC not derived
from charcoalor charredplant materials.

2.5.4 SoilHumus
Soilhumusrefersto theamorphous organicmaterialsremaining in soilsafterextraction of thewater-
soiubiefractionandexclusionof particulate organicmaterials (Fig.2.3).Humusconsists of a mixture
of humicsubstances andnonhumicbiomolecules. In alkalineand neutralsoils,humus dominates the
soil organicfractionbecauseof the rapid decomposition of plant residuesby soil faunaand
microorganisms,In acidicsoils,plantfragmentsmakealargercontribution to thesoilorganicfraction;
however,humusstill represents animportantfractionandcancontributesignificantlyto soilprocesses
(e.g.,podzolization andmineraldissolution). Althoughrecentevidence questions theimportance and
validityof the classicalhumic fractions (Section it
2.5.1.1), is not yet possible to simply dispeltheir
importance in soilsanda discussion of theirchemicalproperties is required.
Soil Organic Matter B-63

2.5.4.1 HumicSubstances
The componentfractions of soil humic substances,humin, humic acid and fulvic acid, exhibit a
continuumof severalchemica]characteristics(Fig. 2.3). Sincethe differentiarionof the threehumic
fractionsis basedsimply on their solubility in alkalineandacid solutions,fractionationproceduresare
methoddependent.Quantitative,reproduciblefractionationcan only be achievedby strict adherence
to a given methodology.Changesin methodology(e.g.,the type and concentrationof solutein the
extractant)cansignificantlyalterthepartitioningof soil humusC into thesefractionsand thechemical
characteristicsobservedfor each fraction (Hayes et al., 1975).A standardextractionmerhodology
exists (Swift,1996) and well-characterizedreferenceand standardhumic substancesare available
from the InternationalHumic Substances Society.
The ability to extractand de-ashsoil humic and fulvic acidsfacilitatedthe acquisitionof detailed
datapertainingto their chemicalcompositionandphysicalproperties.Much lessinformationhasbeen
collectedfor soil humin fractions;however,the introductionof spectroscopicmethodscapableof in
slta anaiysishasenhancedour understandingof the compositionof soil humin (Saiz-Jimenezet al.,
1979; Preston and Newman, 1992). Average chemical formulae for humic and fulvic acids as
suggestedby Steelink( 1985)areC,oH,rOrNandC,rH,rOrN,respectively.Humic acidscontainmore
C and N but less O than fulvic acids. Stevenson(1994) and Swift (1996) have provided detailed
compilations of the chemical methods used to quantify the content of functional groups, the
degradativemethods used to identify structural components,and the physical methods used to
measurepropertiessuchas molecularweight and particlesize.Datacollectedby Schnitzer( 1977)on
the functionalgroupcontentof humic and fulvic acidsextractedfrom soilsfound in differentclimatic
zonesshowed significant variations.Solid-state'rC NMR analysesof humic acids and fulvic acid
fractionsfrom severalsoil typesalso revealedstructuraldifferences(Malcolm, 1990).
Detailed reviews of the chemical compositionand structureand physical propertiesof humic
substances can be found in Oades(1989),Hayeset al. (1989),Stevenson(1994),and Beyer (1996).
On the basisof the informationpresentedin thesereviews,thechemicalandphysicalpropertiesof soil
humic substances can be summarizedas follows: ( 1) aromaticrings are a significantcomponentand
multipie substitution with carboxyl, hydroxyl, carbonyl and alkyl groups exists; (2) signrficant
quantitiesof Ci-C20 alkyl C chainseitherunsubstitutedor substitutedwith O-containingfunctional
groupsarepresent,with smallerchainlengthspredominating;(3) aromaticandalkyl groupsarebound
togetherprincipally by C-C bonds and ether linkagesto form the backbonestructureof the humic
molecules;(4) the aromaticalkyl backbonestructureis randomand is not characterizedby a regular
sequenceof aromatic and alkyl groups;(5) simple and polymeric proteinaceousand carbohydrate
groupsmay be boundto thearomaticalkyi backboneorphysicallyassociated with humic surfaces;and
(6)molecularweightsvary from 103to in excessof 106and the moleculesexist in randomcoils, which
aremore tightly cross-linkedandcoiled in the center.An attemptto combinethesecharacteristics has
led to the generationof chemicalmodelsrepresentativeof an averagestructurefor humic materials
suchas that presentedby Schultenand Schnitzer(1993) for humic acid.
The range in both type and content of function groups,the presenceof numerouschemically
different monomeric components,and the inclusion of biopolymer-like componentsin humrc
structures,suggestthat a variety of different mechanismsmay be involved in their genesis.The
mechanismsof humic substancegenesishave been reviewed (Hatcher and Spiker, 1988; Hedges,
i988; Stevenson,1994;Shevchenkoand Bailey, 1996),and thereis generalconsensus that humic
substancesresult from the transformationof organic plant residues.The proposedmechanismsof
genesiscan be placed within two contrastingcategories:( I ) partial biotic biopolymer degradation,
wherethe integrity of the biopolymeris not destroyed,and the modified biopolymerforms the humic
substancebackbone,and (2) abiotic condensationpolymerization,in which simple products of
B-64 Soil Chemistry

Biotic lliop{,1}'nrcrdegradation
pathwaY Abiotic condensation polymerization
pathway

Rcc!lcitrur{ biopol}mc6 Lrblle blopol-YnFrs

mlinhs protcia& c$bolidrrtes

lncrcasing
cr1ent ol'
con(len\ati0n

prcposed {t}iotl. cordcilirdon ffihstirN

folYphrMl thsr!'
S!!r/rhin. condeairti0.
Phetrol rEd qulnonc formrrlor from mrbohldrrtB
I'hotoridstion of polyio6otuhtcd lipid!

i
COr. H 'O. lf}l.i, crc

Fig. 2.5 Schematic representationof the mechanisms postulated to be involved in the genesis of soil humjc sub-
stances[Based on models presentedby Hedges, 1988 and Hatcher and Spiker, 1988]

biopolymerdegradationrepolymerizeto form humic substances (Fig. 2.5).lt is importantto note,as

suggestedby Hedges( 1988),that the two mechanismsof humic substancegenesisare not mutually
exclusive,since biopolymer degradationis prerequisitefor the abiotic condensationpathway.The
term abiotic is used to refer to the later stepsin the pathway in which chemicalreactionsbetween
simple cornpoundsreleasedby biotic processescondenseto form the humic substances.
In the proposedbiotic biopolymer degradationpathway,recalcitrantmacromoleculesenter the
humin fraction in a partially alteredstate.13CNMR data have indicatedthe presenceof lignin-iike
humin structuresin anaerobicpeats,whereasthe humin fractionof aerobicsoils lacks the methoxyl,
aryl ether, and phenolic groups typical of lignin (Hatcher et al., 1985). Significant quantities of
aliphaticC presumedto originatefrom plant cuticles(Nip et al., 1986b),microbial sources(Hatcher
et al. 1983;Baldocket ai., 1989),or the cleavageof lignin ring structures(Flaig, 1966)arealsopresent
in the soil humin fraction.As theextentof decompositionof humin moleculesincreases, small organlc
fragmentsare releasedand the content of O-containingfunctional groups(carbonyl and hydroxyl)
increaseson the residualmolecule.Such increasesin functionalgroupcontentresult in an increased
extractabiiityof the residualmolecule in alkaline solution, indicativeof a transitionfrom humin to
humic acid. Although similaritiesin chemicalstructurebetweenhumin and humic acids are noted,
humicacidstypicallycontainlessmethoxylandmorecarboxylC thanhumin (Hatcheret al., 1985),
and pyrolysis studiesindicatethat the monomericspeciesof residuallignin structuresin humic acids
exhibit amore advancedstageof decompositionthanthosefound in humin (Saiz-Jiminezetal.,1979).
Further oxidativedegradationfragmentsthe humic acid molecules,and increasesthe contentof O-
bearingfunctional groupsto producefulvic acidsand simple monomericspecies.Ertel and Hedges
(1984)havedemonstratedthat fulvic acidsalso containlignin-derivedstructures,and that the extent
of alterationwas greaterthan that noted for humic acids.To accountfor the N containedin humic
substances,a reaction mechanismhas been proposedwhereby amino groups react with modified
lignin (Stevenson, 1994).
Soil Orpanic Matter B-65

In the abiotic condensationpolymerizationpathway, molecular fragmentsreleasedduring the

decomposition of precursor molecules and/or molecules released as metabolic byproducts from
microorganismspolymerize via chemical reactions.As the molecular weight of the synthesized
polymer increases,a progressionfrom fulvic acid to humic acid to humin occurs. Four abiotic
mechanismshavebeenproposedand schematicrepresentations of the variouschemicalreactionsare
presentedby Hedges(1988) and Stevenson(1994):(l) the polyphenoltheory,(2) the melanoidin
model (a sugar/aminecondensationreaction),(3) pbenolandquinoneformationfrom carbohydrates,
and (4) photo-oxidationof polyunsaturatedlipids. In the polyphenol theory, monomeric phenolic
species(mono-, di-, and trihydroxy phenols)are producedby the enzymaticdegradationof lignin
(Kirk, 1984) or synthesizedby various soil microorganisms(Martin and Haider. 1971). These
monomeric phenolic speciesare capableof forming a quinone structurein the presenceof O, or
polyphenoloxidaseenzymes,which spontaneouslypolymerize with each other or with amines or
ammoniato producepolymericcompounds.Laboratoryexperimentshaveshownquinonesgenerated
from o- andp-polyphenolscondensewith eachother or with amino acidsto form syntheticpolymers
with chemicalstructuressimilar to thoseof naturalhumic substances (Ertel andHedges,1983) In the
melanoidin model, sugars and amines react to form an N-substitutedglucosamine which can
dehydrate,reaffange,or condenseto form simple fragments(e.g.,glyceraldehyde)and structurally'
complexbrown nitrogenouspoiymers.Dark coloredpolymerscan alsoform from carbohydratesat a
similar rate in the absenceof nitrogenouscompounds(Popoff and Theander,l9'761Hedges,1978).
Auto-oxidativecrosslinkingreactionsbetweenpolyunsaturatedfatty acids,inducedby photolysis,
rverepostulatedto be amechanismof humic substance formationin marineenvironments(Harveyand
Boran,1985).Suchreactionsmay help to explainthe presence andpersistence ofhighly crosslinked
alkyl C in terrestrialsystems(Krigel-Knabneret al., l992a,b).

2.5.4.2 NonhumicBiopolymers

Carbohydrates
The chemical structure,properties,and importanceof carbohydratesin soil have beenreviewedby
Cheshire(1979),Oades( I 989), and Stevenson( I 994).Carbohydrates accountfor the largestfraction
of soil organicC found in nonhumicbiopolymers(100-250g kg-'soil organicC). They exhibit a range
in molecular size from simple monosaccharidesto oligosaccharides containing several
monosaccharide of high molecularweight which containlarge numbersof
units, to polysaccharides
monosaccharideunits. Plants contribute directly to the soil carbohydratefraction through the
depositionof simple sugars,hemicelluloseand cellulosein particulateresiduesand various simple
sugarsand polysaccharidesin root exudatesand mucilaginousmaterials.Various products of the
metabolicactivity of soil organismsalso contributeto the soil carbohydratefraction.Theseinclude
extracellularrnucilagesencapsulatingbacteriaand fungi, cell wall structuralpolysaccharides(e.g.,
chitin)(Fi5.2.2).and intracellularpolysaccharides. Relativeto many otherforms of soil organicC,
soil carbohydrates arevulnerableto decompositionunless:( 1)decompositionprocesses arelimited by
environmental conditions; (2) the carbohydratesare buried within a matrix of biochemically
recalcitrantmaterial (e.g., cellulose and/or hemicelluloseburied within a lignin matrix in plant
materials); or (3) the carbohydratesare biologically stabilized by adsorptiononto soil mineral
particlesor by their physicalseparationfrom decomposermicroorganisms.
In peats, forest litter layers and composts, reduced rates of decomposition and.lor the
preponderanceof plant materialslead to a carbohydratefraction dominatedby structuresof plant
origin, whereasin mineral soils the carbohydratefraction is typically dominatedby microbially
8,66 Soil Chemistry

derivedmaterials.Although the carbohydratestructurespresentedfor piant mat€rialsinFig.2.2 are

derivedfrom singlenonosaccharides, the largevarietyof monosar:charides found in soil anddifferent
glycosidiclinkages(e.9.,a, pl-4 and pt-61 givesrise to a potentialfor largevariationsin chemical
structure.However, both Oades(1989) and Stevenson(1994) indicatedthat within any single
polysaccharidernolecule, it is unlikeiy that more than three or four different component
monosaccharides can be identified.
Hydrolysisproceduresresult in the degradationofplant polysaccharidestructuresand the release
oi' various classesof monosaccharidesincluding neutral sugars, amino sugars, acidic sugars,
methylatcdsugars,and sugaralcohols.The neutralsugarsconsistofhexoses(giucose,galactoseand
mannose),pcntoses(arabinoseand xylose),and deoxyhexoses (rhamnoseand fucose)with the
hexoses,particularly glucose, generally accountingfor the largest component (Cheshire, 1979).
Excluding glucose,polysaccharidessynthesizedby microorganismsare dominated by gaiactose,
manose, rhamnose.and fucose. whereas plant polysaccharidescontain appreciablecontents of
arabinose and xylose (Cheshire, 1979). This has led to the use of the galactose+mannose/
xylose+arabinose (g+m/x+a) and rhamnose+fucose/arabinose+xylose (r+f/a+x) ratios as indicesof
the contributionmadeto the soil carbohydratefraction by plantsand microorganisms(Oades,1984;
Murayama, 1994),Values of < 0.5 for the (g+m/x+a) ratio and < 0.01 for the (r+f/a+x) ratio are
indicativeof carbohydratesof plant origin, while respectivevaluesof > 2.0 and > 0.40 are indicatrve
of microbialiy derivedcarbohydrates. Guggenberger et al. ( I 994) usedthesetwo ratiosto examinethe
origin of organic C associatedwith different particle size fractions.The changesin the two ratios
across several land managementtreatmentsindicated an increasedproportion of plant-derived
carbohydratewith increasingparticle size.
Amino sugarsaccountfor 20-60 g kg-' of soil organic C. They are generallyassumedto be of
microbial origin. In excessof 25 different amino sugarsare known to exist as productsof microbial
metabolism(Sharon,1965).Monomeric aminosugarscan be identifiedby chromatographicanalysis
of HCI hydrolysates.The most prevalentof the amino sugarsis D-glucosamine,the monomeric
componentof chitin, theN-acetylglucosamine structuralpolymerfound in fungalmycelia.Significant
quantitiesof D-galactosaminecan also be found in soils,and changesin the ratio of D-glucosamine/
D-galactosaminemay be indicative of the compositionof the microbial decomposercommunity
(Stevenson,1994).The higherratios notedby Sowden(l 959) for acidic soils are consistentwith the
enhancedrelative importanceof fungi in acidic environments.Other amino sugarsidentifiedin soils
includemurarnicacid and D-mannosamine. The dominantforms of theacidicsugars,uronicacids,are
glucuronic and galacturonic acids. Measurementof the contents of these acidic sugars in soil
hydrolysatesis difficult becauseoftheirrapid decarboxylationwhich may resultin lossesin excessof
507o. Using a carbazolemethod of analysis, acidic sugars have been estimated to account for
a p p r o x i m a t e l y- 5 V oo f t h e s o i l o r g a n i c C ; h o w e v e r , G r e e n l a n d a n d O a d e s ( 1 9 7 5 ) c o n s i d e r t h i s t o b e
a minimum value.The methylatedsugars2-O-methyl-L-rhamnose and4-O-methyl-D-gaiactose and
thesugaralcoholsmannitolandinositolhavealsobeenidentifiedin thehydrolysatesofsoils andpeats
t C h e s h i r e1, 9 7 9 )
The O-alkyl or (O-alkyl + di-O-alkyl) region of solid-state trc NMR spectrais often used to
providean estimateof the contentof polysaccharide C in soils.Numerousstudieshavereportedhigher
carbohl'drateC contentsbasedon rrC NMR analysisthan could be accountedfor by wet chemical
hydrolysis followed by quantificationof monosaccharidecontentsof hydrolysates(Ogner, 1985;
Oadeset al., 1987;Prestonet al., l989a,b).For example,Oadeset al. (1987)observedthat in soil
particlesize fractions> 20 pm the contentof O-alkyl C as measuredby t3CNMR was approximately
twice that of carbohydrateC determinedby acid hydrolysisand quantificationof neutral,acidic, and
Soil Organic Matter B-67

aminosugars.Prestonet al. (1989a)found thatO-alkyl C accountedfor 4A-50V0ofthe signalintensity

of particle size fractions of peats,a significantly greaterproportion of the total organic C than was
accountedfor by wet chemicalanalysisof total carbohydrateC. Cheshireet al. (1992) proposedthat
the over estimationof carbohydrateC contentsby r3CNMR analysesresultedfrom the presenceof
secondaryor pseudopolysaccharide structureswhich exhibitedO-alkyl resonances in '3CNMR, well-
defined C-O vibration absorptionbands in IR, and a CH,O elementalcomposition. The pseudo
polysaccharides differed from the normal polysaccharides in that they did not containhydrolyzable
monomeric sugars and did not yield dehydratedsugar derivativeson pyrolysis. Several organic
structuresproposed to account for the pseudo polysaccharidesignals included highly degraded
polysaccharides and melanoidins;however,any structurecontainingC-O bonds,including the three
C atomsin lignin propanoidchains,could give rise to NMR signalswithin the chemicalshift region
typically ascribedto carbohydrateC. The threeoxygenatedpropanoidC atomsof lignin appearover
the chemicalshift rangeof 60-90 ppm in NMR spectra(Hatcher,1987).The useof the termspseudo
or secondarypolysaccharides,therefore,appearsmisleadingsincewhat was really being compared
was the relationshipbetweenthe quantity of organicC found in C-O structuresderived liom many
possiblesourcesversuscarbohydrateC.

Atkyl Compounds
Initial applicationsof solid-statei3CNMR and analyticalpyrolysisto the study of soil organicC and
humic substances showedthat significantamountsof alkyl C werepresentin thesematerials,contrary
to the previous traditional beliefs of a dominanceof aromatic C. Numeroussolid-stater3CNMR
studieshave shown significant increasesin alkyl C contentas the extentof decompositionin peats,
forest litter horizons,compostsand mineral soils increases(Baidock et al., 1997).The majority of
researchaddressingthenatureof soil alkyl C andthe structuralchangesassociated with decomposition
processes hasbeencarriedout on forestsoils.In suchecosystems, the high organicC contentsoflitter
layersandAh horizons,and the reducedpotentialfor organic-mineralinteractionsfacilitatesanalysis
and interpretation.Extension of theseresultsto agricultural mineral soils, especiallyto high clay
contentsoils with large adsorptivecapacities,shouidbe made with caution.
Alkyl C generallyaccountsfor l5-20% of the organicC containedin fresh litter horizonsand 30*
40Vofor the more humified litter horizonsand mineral Ah horizons(K<igel-Knabneret al., 1997b1.
Organicmaterialsderivedfrom a variety of compoundscontainedin piant residuescan contributeto
the fraction of alkyl C. Soil microorganismsalso synthesizealkyl structureslrom nonaliphatrc
substrate(Baldock et al., 1989;Golchin et al., 1996).Alkyl C in soil organicC consistsof the
following compounds(Kogel-Knabneret al., 1992a):(l) solvent extractablefree and bound lipids
(fatty acids, and waxesderived from plants and soil microorganisms),(2) insolublepolvestersand
nonpolyesterscontained in the plant cuticles and walls of cork cells in roots and bark. and (3)
macromoleculessynthesizedby soil microorganisms.
Solventextractablefree and bound lipids accountfor approximately30Vaof the rrC NMR signal
intensityin the alkyl C regionobservedfor forestsoils(Kdgel-Knabneret al.. 1988:Ziegler,1989;
Ziegler and 7,ech, 1989). The chemical nature of free and bound lipids has been discussedby
Stevenson (1994). They include waxes, organic acids, steroids and terpenoids, carotenoids,
porphyrins,glyceridesand phospholipids.The natureofpetroleum etherextractahlefree lipids and
their relationshipsto the original litter materialshave beenexaminedby Almendros et al. (i996).
Thesematerialsarereadily metabolizedby soil microorganismsin forestsoilsand arenot considered
a major contributorto the accumulationof alkyl C in humified structures(Tegelaaret al., 1989;
Ziegier,1989).
B-68 Soil Chemistry

Cutin and suberin(insolublepolyesters)can also be readilydecomposedby thosebacteriaand

fungi that producecutinase.Mammals effectively degradecutin so that contributionsto the soil via
faecaldepositionareminimal (Tegeiaaret al., 1989).Riedereret ai. ( 1993)measuredchangesin the
contentof cutin-derivedmonomersin Fagus sylveticalitterdecomposedfor 446d. Over the first 100
d, the content of cutin monomer C, relea.sedby saponificationof the residual litter, decreased
proportionatelyfasterthanbulk organicC, but thendecreasedat a rate similar to bulk organicC over
the 100-446d period.Similar resultswereobtainedby Ziegler and Zech ( 1990)and Kcigel-Knabner
et al. (1992b)indicatingthat a selectivepreservation ofcutin structureswas not responsiblefor the
increasedproportion of alkyl C noted with increasingextent of decomposition.Further,decreased
concentrationsof cutin and suberinwere notedin progressingfrom litter to well-humified organicand
mineralAh horizonswhen concentrations wereexpressed per unit massof total organrcC (Kdgel
Knabneret al., 1989;Riedereret al., 1993).A selectivepreservation of intactcutin or suberinis.
therefore.not likely to contribute to the increasedproportion of alkyl C observedwith increasing
extentof decomposition;however,microbiallyor chemicallytransformedcutin and suberinmat'
accunrulate.
Nonsaponifiablecutan and suberan(insolublenonpolyesters)appearto be resistantto biological
andchemicaldegradation(Tcgelaaretal.,1989)andalthoughpresentatlowconcentrationsinplant
residues,concentrationby selectivepreservationcould representa mechanismfor the accumulationof
alkyl C in soils.RiedererandSchrjnherr ( l988) notedthatthe nonpolyester fractionof CIiviaminiatt"
Reg. cuticle increased with ontogenetic development through a continuous transformation of
polyestercutin into nonpolyestercutan.Such a reactionmay be occurringvia a photo-oxidatil'e
crosslinkingmechanism,similar to that proposedby Harvey and Boran (1985) for the genesiso1
marinehumic substances. Kdgel-Knabneretal. ( l992a,b)usedacombinationof selectivedegradation
techniquesand ID rrC NMR to distinguishbetweenmobile (little crosslinking)and rigid (highll
crosslinked)fonns of nonsaponifiablealkyl C in forestsoils.Freshtbrestiitters contained55-60Voot
their C in rigid structures and 4045o/o in mobile structures.With the increasing extent oi
decompositionthemobile fractionwas lost andtheOh andAh nonsaponifiablealkyl C wascomposed
almos{.exclusivelyof rigid structures.Possiblemechanismsthat may accountfor such a conversion
duringdecomposition processes include(1) a selectivepreservation ofrigid structurespresentin the
initial plant residues,(2) the productionof rigid metabolicproductsof microbial origin synthesized
during decomposition,and/or (3) the conversionof mobile alkyl C to rigid alkyl C, with enhanced
cross-linkingbeing induced by chemical,physical or biological processes.In addition, rigidity as
assessedby ID IrC NMR may be influenced by adsorptiononto mineral surfaces;however, this
rcmains to be determined. ID rrc NMR spectra acquired, for a bulk culture of intact soil
microorganismsand their nonsaponifiablealkyl rcsidues,indicatedthe presenceof both mobile and
rigid structures(Kbgel-Knabner et al. 1992a).In a more detailed application of ID 13CNMR tc
characterizinguntreatedintactculturesof soil microorganisms,Baldocket al. ( 1990b)found that I 3%
of fungal and66Voof bacterialalkyl C exemplifieda rigid structure.
On the basisof the resuitsoLrtained from forestsoils,the increasein alkyl C during decomposition
appearsto resultfrom an accumulationof nonsaponifiablerigid structureswhich may originatefrom
selectivepreservationof plant and microbial residuesor be producedin situ via biological and/or
chemicaltransformationsof existingalkyl structures.In soils with appreciablemineral surfaceareas.
the potentialexistsfor other forms of alkyl C (extractablefree and boundlipids and cutin and suberin
polyesters)to contribute through a biological stabilizationimparted by adsorptiononto minerai
surfaces.Supportingevidencefor the importanceof adsorptionreactionswith mineral surfacesis
provided by the data of Oades et al. (i987) and Baldock et al. (1992). They found significant
Soil OrganicMatter 8-69

accumulationsof alkyl C in thefine particlesizefractions,with a largehighly reactivesurfacearea,for

a rangeof mineralsoilsincludingan Alfisol, two Mollisolsand rwo Oxisols.

Lignin
The chemicalcompositionof lignin and its residuesin soil is a functionof its initial chemicalstructure
and the extent of modification by soil organisms.Lignin is generallymore resistantto biological
decompositionthan the other major biopolymersfound in plant residues.becauseof its chemical
structure (Fig. 2.2). The most efficient lignin degrading organisms are the group of aerobic
filamentousbasidiomycetescollectiveiyreferredto as white rot fungi. Theseorganismsfragmentthe
lignin polymer at irregular positionswithin both the side-chainand aromaticrins srructuresby the
synthesisandexcretionof enzymeswhich catalysefree radicalformation(Haider. 1992r Kirk. 1987).
Brown rot basidiomycetesdo not fragment the lignin polymer extensively. but are capable of
demethylatingmethoxyl groups on the guaiacylor syringyl units to produceo-hrdroquinonoid
structureswhich can be easily oxidized to quinones. The quinone structurescan lhen jnduce
condensationreactionsasdiscussedforthepolyphenoltheory.Forplantlitter,itisgeneralll assumed
that basidiomycetes, similar to the white rot fungi, aid in lignin decompositionafter other orsanisms
haveremovedthe more labile components.Bacteriaplay a smallerrole in lignin degradarion.bur as
notedfor the brown rot fungi, they can modify the natureof functionalgroupsattachedto the lignrn
polymer. Organismsdo not gain energyor metabolitesfrom lignin degradation(Haider. 199-l).but
benefit through an exposureof labile cellulose and hemicelluloseburied within the lignin/
polysaccharidematrix. The role of variousorganismsand the mechanismsof lignin degradarionhave
beendiscussedrecentlyby Shevcheikoand Bailey (1996)and Hammel(1997).
The chemicalstateof lignin in plant residuesand soils has beenexaminedby spectroscopicand
chemicaldegradativemethods.Hatcher(1987) presentedsolid-stater3C NMR spectraof isolated
naturallignin. On the basisof this work and others,the signalsfrom eachof the varioustypes of C
containedin lignin polymerscan be assignedas follows: 56 ppm = methoxyl C, 60-90 ppm = propl,l
side-chain O-alkylC, 105-145ppm = C- andH-substituted aromaticC, and 145-160ppm = phenolic
C. The chemicalshift valuesand form of the phenolicpeakcan be usedto provideinformation on the
type of lignin monornerspresent.The aromaticC-O associatedwith the methoxyl group of guaiacy'l
unitsappearsat 148 ppm while that of syringyl units appearsat 153 ppm. Thus, softwoodlignin,
dominatedby guaiacylmonomerswould exhibit a phenolicpeak at 148 ppm, hardwoodlignin
containingboth guaiacyl and syringyl monomersexhibitstwo peaksat 148 and 153 ppm, and grass
lignin dominatedby syringyl monomersexhibitsa peakat 153ppm. On average,of the l0-1 I C atoms
containedin the two major lignin monomers(guaiacylandsyringyl),2-3 arephenolic,3-4 areC- and
H-substitutedaromatic, 3 are O-alkyl, and 1-2 are methoxyl. The actual values depend on the
distributionof the two major monomericspecies(guaiacyland syringyl) (Pig.2.2) and the natureof
ihe bondsbetweenmonomericunits.Significantdeviationsfrom thesevalueswould be indicativeof
how the averagelignin moleculewas alteredby decompositionprocesses.
In soilsand peats,lignin isjust one componentofthe decomposing residuesand severalsignals
from other types of C overlap and mask changesin the lignin structure.The propaneside-chainC
signalsare completely hidden by the C-O C of carbohydrates,and amine C overlapsthe methoxyl
s i g n a l s . F o r t h e m e t h o xs yi gl n a l , h o w e v e r , t h e i D r s C N M R p u l s e s e q u e n c e c a n b e u s e d t o d i f f e r e n t i a t e
betweenthe sontentof methoxyl and amineC. The ID pulsesequencecan also be usedto determine
the averageamountof protonatedversusnonprotonatedaromaticC. Readersarereferredto Hatcher
(1987) for an excellent example of the applicationof ID to the study of lignin. Decreasesin the
proportionsof phenolicand methoxylC are typical of theresultsobtainedwhen solid-stater3CNMR
hasbeenusedto characterizethe chemistryoforganic C in soil fractionsofdecreasingparticle size
B-70 Soil Chemistry

(Oadeset al.. 1987: Baldock et al., 1992; Guggenberger et al., 1995a).Such observationsare
consistentuith the observedpatternsof decompositionnoted for bacteria and brown rot fungt
decornposing plantresiduesmentionedabove.Nevertheless, adegrceof uncertainty existswith solid-
slate'r C NNIR databecausethe analysisdoesnot indicateconclusivelyfrom which structuresthe
\ . i r i ( \ r . rt 1
i p c so l ' C w e r ed e r i v e d .
Lignin degradationis most eff'ectivelyexamined by proceduresthat quantitatively break the
Iinkagesbetweencomponentmonomersand measuretheamountof eachtype of monomer.Two such
methods are an alkaline CUO oxidation procedure (Hedges and Ertel, 1982) and a
tetranrethylammonium hydroxide(TMAH) thermochemolysis procedure(Hatcheret al., 1995).In
both proceduresthe lignin polymer is fragmentedinto its componentmonomers,which areseparated
and quantified using reversephasehigh performanceliquid chromatography(Krigel and Bochter,
1985).gaschromatography (Hedgesand Ertel, 1982;Baldocket al., 1991)or gaschromatography-
massspectrometry (Hatcheret al., 1995).
The CuO-oxidationprocedurehas beenshown to release25-90Voof the Iignin C in the form of
simplephenolicmonomericstructures,dependingon th€ typesof lignin monomersinvolved (Hedges
and Ertel, 1982;Ertel and Hedges,1984).A comparisonof the tignincontentsbetweensamplescan
be madeby surnmingthecontentsof the guaiacyl,syringyland p-hydroxyphenolderivatizedreaction
products.The ratio of the quantityof acidic to aldehydicforms of eachmonomer(Ac/Al) can give an
indication of the stateof decompositionor structuralalterationof each monomeric unit within the
l i g n i n p o l y m e r , o r otfh e e n t i r e p o l y m e r ( E r taenl d H e d g e s1,9 8 4 ; E r t e l e t a l1. ,9 8 4 M
; o r a n e t a l .1 9 9 1 ) .
The ratio of lignin-derived dimerslmonomerspresentin CuO oxidation products of sedimentary
l i g n i n s h a s a l s o b e e n u s e d a s a m e a s u r e o f t h e e x t e n t o f f u n g a l - i n d u c e d d e g r a d aettiaoln. ,(1G9o9n3i) .
Scveralrecentexamplesof the applicationof theCuO oxidationmethodologyto the studyof lignin
in variousformsof soil organicC includework competedby deMontignyet al. ( 1993),Guggenberger
etal. (1994a)and Amelung andZech(i996). deMontignyet al. (1993)studiedthe extentof lignin
alterationin nonwoodyand woody foresthorizons.In progressingfrom the surfacefibric to the more
humitied humic layer of the nonwoody horizons,little changein the total amount of phenolic C
releasedwas noted (3 l-33.5 g kg-'organic C); however, the guaiacyl Ac/Al ratio increased
significantly from 0.43 to 1.01, suggestingthat, although the lignin content did not change
significantly,it becamemore structurallymodified with increasingdepth,andpresumablyforestfloor
residencetime. The CUOoxidationproductsof lignin containedin particlesizefractions(sand,silt and
clay liactions) in mineral soil collectedfrom four different ecosystemsshoweda decreasein lignin
contentand an increasein the extentof lignin alterationwith decreasingparticle size (Guggenberger
et al., 1994).Amelung andZech( 1996)selectivelyremovedthe external0.5 mm of soil pedsandused
CuO oxidationto examinetheamountandstateof decompositionof lignin in soil from the pedsurface
andped interior.The sumof the lignin-derivedphenoliccompoundswas significantlylessfor the ped
surfacethanped interior soil, suggestingan enhancedextentoftignin decompositionat ped surfaces.
The increasedAc/Al ratios for guaiacyl and syringyl monomersand the selectiveloss of the more
easily decomposablesyringyl monomersin ped surfacesoil supportedthe hypothesisof enhanced
oxidativedecompositionat ped surfacesrelative to ped interiors.
The TMAH thermochemolysis procedureis analogousto theCuO oxidationprocessexceptthatthe
derivativesare methylatedand ready for direct injection into a GC or GC/lvISsystem.Hatcheret al.
(1995) comparedthe results of the TMAH and CuO oxidation methods when performed on the
samplesanalysedby deMontigny et al. (1993). The distribution of products obtained with both
analyseswas similar, asevidencedby a linearcorrelationbetweenthe AclAl ratiosobtainedusingthe
two methods.However, the TMAH method provided a more sensitiveindicator of the extent of
decompositionbecauseof the larger rangeof valuesobtained.The TMAH methodalso resultedin a
Soil Organic Matter B-7r

greater preservationof monomer side-chainstructuresthan the CuO oxidation. It is, therefore,

importantin the TMAH analysisto include all the variousderivativescontainingmethoxylatedside
chains, when estimatingthe amount of C containedin lignin structuresfrom the products of the
thermochemolysisreaction.The enhancedpreservationof the side-chainstructuresmay, with further
research,be utilized to provide additionalstructuralinformationpertainingto the lignin polymer and
its alterationthrough decomposition.Additional studiesthat have utilized the TMAH procedureto
examinethe amount and extent of decompositionof lignin have thus far concentratedon relatively
purenaturalorganicmaterials(Baldock etal.,1997:Nanny ,1991. Personnalcommunication;andits
extensionto mineralsoilsor mineralsoil fractionshasnot yet occurred.Baldock et al. (1991I usedthe
TMAH procedure in conjunction with solid-state'3C NMR to examine the chemrcal changes
associatedwith the decomposition of three species of wood exhibiting different stages of
decomposition.The two analyticaltechniqueswere complementary,but the TMAH resultsshowed
thatsignificantalterationsto thestructureoflignin could occurbeforesignificantchangesin theN\IR
spectralintensitiesbecameapparent.

2.6 Conclusions
The diverse chemical nature of soil organic C contributesto the important role which it plays in
defining the magnitude of a variety of soil propefiies and processes,and has made its selective
chemical characterizationchallenging.The continual developmentof new technologiesand ne*
proceduresor applicationsofexisting technologiescapableofstudying the propertiesand chemical
characteristicsof soil organicC in situ, will undoubtedlyfurther advanceour understandingofthis
important soil component.Severalresearchareaswhich offer significant potentiai are (l) further
developmentand use of methods which can selectivelycharacterizethe chemical composition of
SOM in siru and thusavoid the useof chemicalextractants,(2) definition of relationshipsbetweenthe
speciescompositionof the decomposercommunity andtheresultantchangesin chemicalstructureof
plant residues and soil organic materiais, (3) identification and quantification of biologically
significantpools of C and the importanceof thesepools in defining the magnitudeof soil properties
and processes,(4) quantification of the capacity of soils to protect organic materials from
mineralizationthroughidentificationandmeasurement of therole of soil mineralcomponentsandsoil
architecture,and (5) renewed applicationof wet chemical moiecular techniquesto the study and
quantificationof the contentsof specific classesof biomoleculesfound in soil organic fractions,
particulariyin associationwith quantitativeapplicationsof spectroscopictechniques(solid-stater3C
NMR). In particular,work is requiredto addresstheproblemsassociatedwith identifying the pseudo-
polysaccharideand the unidentifiedorganicN fractions.

Acknowledgments
Useful suggestionsand improvementsto the manuscriptmade by Jeff Ladd. Ron Smernick, Jan
Skjemstadand the editorsare gratefullyacknowledged.

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