ChapterI

Productionand Accumulationof OreanicMatter

The OrganicCarbonCycle

Production, accumulationand preservationof undegradedorganic matter are

"organic
prerequisites for the existenceof petroleumsourcetocks.The term
matter" or "organic material",as usedin this book, referssolelyto material
comprisedof organicmoleculesin monomericor polymericform deriveddirectly
or indirectly from the organicpart of organisms.Mineral skeletalparts, suchas
shells,bones,and teeth are not included.First, organic matter has to be
synthesized by livingorganisms andthereafterit mustbe depositedandpreserved
in sediments.Dependingon furthergeologicalevents,part of the sedimentary
organicmatter may be transformedinto petroleum-likecompounds.It is im-
portant to realizethat during the historyof the earth the conditionsfor syn-
thesis,deposition.andpreservation of organicmatterhaschangedconsiderably.

- The Basisfor MassProductionof Organic

I .1 Photosynthesis
Matter
The emergence of photosynthesis as a worldwidephenomenon is a noteworthy
historical event with respectto the formation of potential sourcerocks. Tbe
photosyntheticprocessconvertslight energyinto chemicalenergy.Photosynthe-
sis is basicallya transferof hydrogenfrom water to carbondioxideto produce
organicmatter in the form of glucoseand oxygen.The oxygenis freed from the
water molecule and not from carbon dioxide. From glucose,autotrophic
organismscan synthetizepolysaccharides, suchas celluloseand starch,and all
other necessary constituents.A simpleform of the equationof photosynthesis
reactionis givenin FigureI.1.1.

u,----cuH'rou.60;-6H2o
6 co2 -t2H2d j,
674 kcal
( Glucose)

r
Polysaccharides

Fig. I.1.1. Equati()l) of ph()toslrnthesis.

Glucose. relatively rich in errergy,is formed by
green plants with the help of sunlight (h . v). Oxygen is by-product of this proccss
 Productionand Accumulation of Organic Matter. The Organic Carbon Cyclc

,\

nfi-"s "
9HzFF ,rt:f
'\(,"r'' H-c. i'-
I I
N
H N H N
,- t:9,l
I
l,i-cl \c:cn
-ru.
-.4c\ -.)\^,,,'k - zc7.t'k-.7t 1-.7tq.,t*. "l .' '":1"
0
t . t . l
cH3 cH: cH3 chg HC:CH

lsoprenoidside chain b P o r p h i nn u c l e u s

Fig. I.1.2. (a) Molecule of chlorophyll. rhe light-absorbinggreen pigment ofplantsand a

prerequisite for photosynthesis.The phytyl side chain of the chlorophyll moleculc is an
important source for chainJike isoprenoid compounds in sediments and oils. Likewise. the
nitrogen-containing porphin nucleus is the precursor for porphyrins. (b) Structure of
Dorphin nucleus

Photosynthesisis the basic processthat accomplishes the massproduction of

organicmatter on earth. Primitive autotrophic organisms,suchasphotosynthetic
bacteriaandblue-greenalgae,werethe first organisms responsible for thismass
production.A basicprerequisitefor photosynthesisis the light-absorbinggreen
pigmentchlorophyll(Fig.I.1.2).In primitiveautotrophsit occursin a relatively
free state in the cell of the organism.In more highly evolvedplants it is
concentratedin chloroplastsin green leaves.These chloroplastsare complete
photosyntheticfactories.
The oldestrecordedformsof organiclife areabout3.1 to 3.3billionyearsold
and are bacteriaand algae-likebodiesfrom the SwazilandGroup in SouthAfrica
(Schopfet al., 1965).However,it is possiblethat life on earthis at leastasold as
the oldestknownrocks- 3.7 billion years.
It is assumedthat approximately2 billion yearsago,photosyntheticproduction
of organicmatter was fairly well establishedworldwide,and this time servesasa
zero referencepoint. Before it was reached,anotherbillion yearsprobably was
required for the isolated occurencesof most primitive organismsto spread
sufficientlyfor photosynthesisand,hence,for massproductionof organicmatter
to be universally prevalent.
A summaryof geologicaleventsconsideredto be importantin the organic
carbon cycle is presentedin Figure I.1.3. Without water there is no life.
Therefore,abundantlife, evenon a mostprimitive level,wasnot possibleon earth
prior to about4 billion yearsago,whenwater becamea commonsubstanceon the
earth'ssurface.During that primordialtime,the atmosphere wasreducing,i. e.,
there waspracticallyno free oxygen.
 -The
1.I Photosvnthesis Basisfor MassProductionof OrsanicMatter

Tim. in
Fig. I.1.3. Events sup-
million
G.ologic l m p o r la n l . v c n t s d u r i n g posedto be of importance
hislory ot th..arih for the evolution of life
during the earth'shistory.
Mass production of orga-
nic matteronearthdid not

l,
500
occur prior to 2 billion
1000
yearsago when photosyn-
thesiswasestablishedas a
l3 worldwide phenomenon
1500 :l
;t:
2000 :
: .! ;
2500
E
Bact.ria and p miliv.
3000 alga.
A b i o l o g i c a l -c h . m i c a l

3500 End ot firsl q.osyn-

t 00 0
Larg.r quantiti.s of
wat.r on surtac. ol
a500
Origin of .arth

It is generally agreedthat the early earth's atmospherewas devoid of free

oxygen,and that it contained H2,CHa,NH3,N2 and HrO. However,this view is
not unopposed,the methane-ammonia hypothesisbeingespeciallyquestioned.In
connection with this hypothesis,Calvin (1969) relers to an abiological or
chemicalevolution that started more than,1 billion yearsago. When primitive
organismsfirst appearedabout 3 billion years ago, they probably utilized the
abiologically produced organic molecules as a source of energy to maintain
metabolism.Therefore, the first organismsare assumedto have been hetero-
trophic. However,the growingpopulationof heterotrophsprobablycouldnot be
supportedforever in this way. It is arguedthat, by the time theseorganismshad
almost depletedthe reservoirof abiologicallyproducedorganic matter, photo-
synthesisdevelopedas a secondsourceof energy.
In this way, heterotrophicorganismsthat were ableto usesunlightasan extra
sourceof energy could becomeindependent,and with further evolution could
escapethe food shortage.Certainpurpie-coloredbacterialiving todayshowthese
properties.They can act like heterotrophsand utilize organic compounds,and
they alsocontain the greenpigmentchlorophyll to carry on photosynthesis. The
oldest form of photosynthesis,asperformed by bacteria, did not produceorygen.
Photosyntheticbacteria are anaerobic.Instead of using HrO as a hydrogen
donor, they can use H2Sand excretesulfur rather than oxygen.
 6 Productionand Accumulation of Organic Matter. The Organic Carbon Cycle

Certain
-blue-greenalgaethat evolvedfrom photosyntheticbacteriaprobably
w€re the first oxygen-producingorganisms.Although there are a number of
photosynthetic pigments,nonecancompletelyreplacechlorophyll(Fig.I.1.2)in
photosyntheticorganisms.Chlorophyll moleculesabsorb light energy, which
elevateselectronsto a higher energylevel. This gain in energyis transferredto
other molecules.
Oxygen is believedto have been toxic to organismsof that time. However, a
reducing environment assured that divalent iron was abundant in aoueous
solutions.This iron could act asa sink for the oxygenproducedasa by-productof
photosynthesis.It is very likely that the well-known banded ironstonesof the
Precambrian are formed by this interplay between photosynthesisand a
subsequentoxidation of iron to a trivalent form, with precipitation of the
insolubleoxides(Cloud,1968).
Autotrophic, photosyntheticorganismswere superior to heterotrophsand
consequentlysoon dominated the biological realm. As stated before, about 2
billion yearsago,photosynthesis emergedasa worldwidephenomenon.Herewith
the foundationfor the food pyramid and the evolutionoahiqherforms of life was
laid. It is arguedthat afterthiseventthe atmosphere of the earthslowlybecame
oxidizing,i. e., free molecularoxygenbecameavailable.
Photosynthesis makesuseof lhe energycomingfrom sunlight,employingonly
a narrowbandof the sun'stotal radiation.The portionof thespectrum utilizid by
most photosyntheticorganismsis between40fi0 16g966 A. which nearlveouals
the portion of light visible to the humaneye.Rayswith shorterwavelengthsand
higher energyare evenharmful to life. Different partsof the visiblelignt spectrum
may be utilized_by different photosyntheticorganisms.The poriion-used is
rleterminedby the type of pigment an organismemploys(Fig. I.1.4). Ir enables
photosyntheticalgaeandbacteriato live at clifferentdepthlevelsin the samebodv
of water.Life in deeperwateris correlativeto useof iongerwavelengths.

- Green algae
....... Greenbacteria
- - Red algae
--- Purple bacteria

Fig. I.1.4. Differentpans

.9 of the light spectrummay
be utilized by different
o photosyntheticorganisms.
This enables photosyn-
thetic algaeandbacteriato
live at differentdepth le-
.u vels in the same body of
nl
water. (Adapted from
E. Tappan and Loeblich,
1970; reprintedwith per-
missionand from publica-
tion of the GeologicalSo-
length in Angstrijm unit s ciety of America)
 '7
1.2The OrganicCarbonBudgetDuringthe History of the Earth

1.2 The OrganicCarbonBudgetDuring the History of the Earth

For a massbalanceof carbon used in photosynthesisduring the history of the

earth, it is necessaryto add up all organic carbon presenton earth in various
repositories,suchas oceanwatersandsediments.The total estimatedamountof
organic carbon and graphite, which formerly representedsedimentaryorganic
carbon,is approximately 6.4 x 10151 (Welte,1970).A morerecentestimateby
Hunt (1972) is about twice as high. However, Hunt includes in his balance
calculation"organic" carbon in basalticand other volcanic rocks, as well as in
granitic and all metamorphic rocks. The biological origin of much of this
"organic" carbon is questionable.
Most of the carbonon earth is concenlratedin sedimentaryrocksof the earth's
crusl. Part of it is fixed asorganiccarbon,and a greaterpart ascarbonatecarbon.
It is estimatedthat 187oof total carbonin sedimentaryrocksis organiccarbonand
that 827oof sedimentarycarbonis bound in the form of carbonates(Schidlowski
e t a l . ,1 9 7 4 ) .
A relationshipof courseexistsbetweenorganiccarbonand carbonatecarbon.
The atmosphericCO2-reservoiris in a constantexchangewith the hydrospheric
CO2-reservoir.From aquaticenvironments,carbonatesmay be precipitatedor
depositedby organisms(shells,skeletonsetc.) to form carbonatesediments.
Conversely,carbonaterocks may be dissolvedto contribute to the equilibrium
reactionbetween CO3 , HCO; and CO2 in waters.Primary organic matter is
formed directly from the atmosphericreservoir by terrestrial plants, or by
photosynthesisof marine plants from dissolved CO, in the hydrosphere.
Terrestrial and marine organicmatter, in tum, is largelydestroyedby oxidation.
Thus CO, is returned for re-circulation in the system. A simplified sketch
showingthe main processesand pathwaysconcemingthe elementcarbonin the
earth's crust is given in Figure I..1.5.Only an almost negligibleportion of the
organic carbon in the earth's crust, including the hydrosphere,is found in
living organismsand in a dissolvedstate.The major part of the organiccarbon
(5.0 x 10'st) is fixed in sediments. Another sizeablepart ofthe organiccarbon
(1.4 x 10'50,mainly,in theformof graphite-like materialor metaanthracite, is
fixed in metamorphicrocks of sedimentaryorigin (Table I.1.1).
If it is correct that all this organic carbon has been formed either directly or
indirectly by photosynthesisduring the earth'shistory,there shouldhavebeen a
correspondingamount of oxygen liberated simultaneouslyaccording to the
equationof photosynthesis(Fig. I.1.1). This amount must be accountedfor by
free oxygen, together with formerly free orygen presentlyused by oxidation
processesof substanceother than biologicalorganicmatter. At present,we find
free oxygen in the atmosphere (in air 20.95 vol 7o) and varying amounts
dissolvedin oceanwaters(generalrange2-8 ml Or per l). Formerly free oxygen
is found in both dead and living organic matter. However, most formerly free
oxygenhasbeenutilized by the oxidation of variousformsof sulfur andiron. This
oxygenis bound today in sulfatesand in oxidesof trivalentiron, andis distributed
throughoutthe earth'scrust, includingthe hydrosphere(Table I 1.2).
As statedbefore,it is believedthat the primordial atmosphereof the earthwas
reducingandthe elementssulfur andiron occurredonly in divalentform. Oxygen
 Producrion and Accumulation of Organic Matter. The OrsanicCarbon Cvcle

""9i, : ;
r E:i;!
I

rt.o.6!j
;.!
.:i..'f
.1*. €
'E 9 ;
c l 9 ; " g t
I :.9
E 6
! 1 d -
c :

g
-i+
= :-.
S
; 9
\ .E;
c ; i

./t i'

> 5

:
2 / i ,

- :id \ )\
':i
c9r-
!
1"\ >,x ?
iE:
s\
e:l 5
E .

A.a o
9 / 9

d i i F c

f,!

produced by photosynthesis,therefore,was usedto oxidize sulfidesto sulfates

and divalent to trivalent iron. The total free and formerly free oxygenfound on
earthamounlsto approximately 16.9 x 10t5t.
1.2The OrganicCarbonBudgetDuringthe Historyof theEarth

in I0 lst.
TablcI.l. t. Organiccarbonin theearth'scrustexpressed
(After wcltc. 1970)

Organisms and dissolved organic C 0.003

Sediments 5.0
Metamorphic rocks of sedimentary origin
(80% of all melamorphic rocks) 1.4
Total organic cartx)n

Table I.1.2. Frce and formerly free oxygen in the earth's crust.
cxpressedin l0 l st exclusivctlf oxygen in carbonatesand silicates
(After weltc. 1970)

Atmosphere 1.18
Occans 0.02
Biological CO2 0.l6
Dissolvedmarine SOI 2.6
Evaporitic SOa2 10.2
FeO '--- Fe2O3 2.1
Total oxygen 16.9

The ratio of the total quantitiescalculatedfor oxygen(16.9 x 10'st) and

organiccarbon(6.4 x 10r5t)is similarto the massratio of theseelementsin the
CO, molecule:

rOr 32 ^..\
\c 12 |
I formerlyfree oxygenX 10r5t 16.9 \
t -c";t. carbont.
organic"*b"t rocks x 10''
in ...k= [0rst 6.4 l

This balance calculation for oxygen and organic carbon on the basis of
photosynthesisindicatesto us that most of the oxygennot bound in carbonates
and silicateshas indeed been produced by photosynthesis.Therefore, there
should be a relationshipbetweenorganiccarbon in fossilsedimentsand oxygen
levelsol paleoatmorpheres.
Making use of so-calledhalf-massagesof sedimentaryrocks,as givenby
Garrels and Mackenzie(1969), an accumulationrate for organiccarbonof
approximately3.2 x 106t y I was calculatedon the basisof the previously
mentionednumbers.The presentannualmarineproductionof organiccarbonis
estimatedto be 6 x 1010t(Vallentyne,1965). With this annual marine
-4,
production,the total globalpreservation of organiccarbonof 10 or 0.01%
during the earth'shistorycan be calculated.Although it is difficult to estimatethe
true preservation, it seemsto be safeto assumethat it is lessthan0.17o.Menzel
and Ryther (1970)alsoestimatedthat about0.17oof the annualproductionof
organic matter is buried in surfacesediments.Only this tiny fraction of organic
[0 Productionand Accumulationof Organic Matter. The OrganicCarbon Cycle

matter is preservedin sediments,whereasthe remainderis recycled,mainlyin the

euphoticzone of the top water layer in the oceans.This is why oceanographers
speakof a closedsystemwith respectto living phytoplanktonand CO2in ocean
waters.In a studyon the origin andfateof organicmatter in the Black Sea,Deuser
(1971) found a preservationrate of 4o/c.However, this value of 47o has to be
considered as an upper limit, which is reached only under such favorable
condilionsasare found in the Black Sea.Theseconditionsare anoxygen-freeand
fairly calm water body without scavengingbenthic life at the bottom exceptfor
anaerobicbacteria.The sedimentationof certainpetroleumsourcerockshasvery
likely takenplaceundersimilarconditions.
In this connectionthere is frequentlyan alternationofenvironmentsfavorable
for production and preservationof organicmatter and those in which much less
organicmatter is preservedin sediments.A Soodexampleof this is the seriesof
finely laminatedsediments,with altemating layersrespectivelyrich and poor in
organic carbon, describedby Ross and Degens (1974) in young Black Sea
sediments.
The cycle of organic carbon in nature is shown in Figure I.1.6 There is a
p r i m a r ys, m a l lc y c l e( 1 ) w i t h a t u r n o \ . cor f a b o u t2 . 7 t o 3 . 0 x 1 0 1 2otf o r g a n i c
carbon,anda half-lifeof daysup to tensof years.Thereis alsoa secondary,large
cycle(2) comprisingan estimatedquantityof 6.4 x 101st, andwith a half-lifeof
several million years. The two cycles are interconnected by the tiny leakageof

o f o r g a n icca r b o n
Cycle

0rganic mall.t tix.d

in tossll sedrm.nis,
c0al and kero9.n

soils andx.dimcntsr
profoundly Rll.r.d.

0.ad planls,anrmals
0 r g a n i cm a t l . r I n
m . t a m o r p h i cs . d r m . n t s ,
mainly as malaanthra$t.
and graphil..

Cycle
I C y c l e2
Fig. L1.6. The tow major cycles of organic carbon on earth. Organic carbon is mainly
recyclcdin cycle 1. The crossoverfrom cycle I to cycle 2 is a tiny leak that am')unt\ only tt)
0.Ol -0.1 7. to the primary organic productivity ( Afier weltc' 1970)
1.3The Organic Carbon Budget in the Black Sea

about 0.017oto 0.17c of the total organiccarbon,representing oxidationof

sedimentaryorganicmatter to COr. For our considerations, the largersecondary
cycleis of greaterimportance.Once the organic matter hasentereda sediment,
its long-termfate is mainlvgovemedby tectonicevents.In otherwords,phases
of subsidence and increasein burial,or phasesof uplilt and erosion,determine
whether the organic content of a sedimenl is preservedand transformedinto
petroleum, or is eroded and oxidized. If organic matter completesthe second
cycleduringthe birth. evolution.andendof a geosyncline,it undergoesincreasing
burial, andis subjectedto diagenesis.
catagenesis, andfinally metamorphism.The
processes of diagenesisand catagenesisare of prime importancein the formation
of petroleum.

1.3 The OrganicCarbonBudgetin the Black Sea

The BlackSeamayservehereasa modelcase forconditionsprevailingduringthe

formation of sourcerock-typesediments.The subsequentconsiderationsfollow
mainlythe findingsand thoughtsof Deuser( I 97 I ).
In the Black Sea,the main sourceof organicmatter is in situ pholosynthesis
(Fig.I.1.7).A dominantroleis playedby thesmallest unicellularalgae.The main
groupsof marine life dependdirectly or indirectlyupon their rate of production.
About 100 g organiccarbonm 'yr-' have been producedby photosynthetic
organismsover the entire water-coveredarea during the last 2000 years.In
addition, a certainamountof organiccarbon(lessthan 107o)is introducedmainly
as detrital material by rivers and the Seasof Azov and Marmara. Shimkusand
Trimonis(1974)estimated the contributionof organiccarbonto theBlackSeaby
rivers to be about one third of the total input. Furthermore,chemosynthesis
servesas a sourceof organiccarbon.This is the organiccarbonresynthesized by
autotrophicbacteria,the amountof which is not known exactly.Il is estimatedto
be lessthan 15gCo,, m-2yr r.
Most of the organic carbon produced in and carried into the Black Sea is
oxidizedto CO2 in the top 200 m due to respiration,and is returnedto the
hydrosphere-atmospheresystem. The amount immediately returned to the
primary organiccarboncycle(Fig. I.1.6) and thus availableagainfor photosyn-
thesis,is probablycloseto 8070.A smallportion is alsocarriedawayinto the Seas
of Marmara and Azov. The remainderis lransferredinto the anoxicwatersbelow
the top 200 m zone.There it is subjectmainlyto chemicaland microbialattack.It
seemssafeto assumethat generally80o/oto95Vo otthe organiccarbonis recycled
in the top water column, where there is photosyntheticactivity.
In the anoxiczone, Deuser (1971) assumeda steady-state situation.The
organic matter being oxidized due to sulfate reduction,and due to lossesfrom
solubilizationand fossilizationis balancedby an equal influx of organicmatter
from above,where oxygen-bearingwatersprevail.
About one fourth of the organiccarbonintroducedinto the anoxiczoneof the
Black Seais buried in the sediments.and thusfossilized.This amountsto asmuch
as 470 of the total organiccarbon input of the Black Sea.This is certainly more
12 ProductionandAccumulationofOrganicMatter'The OrganicCarbonCycle

c a t t e ri n B l a c kS e a
S o u r c eosf 0 r g a n im
Photosy.thesis

N{' /../S
wiih 02

. C h €m o s y n t h e s i s

with H2S.

i ca t t eirn B l a c S
t a t eo f o r g a n m k ea
Respiration Seas of Azov and

N.-
\st

P a r t i c u l a t e F l ux

0 x r d a l i o n{ d u r i n gS 0 1
S o l u b i lz a l

Sclm2lyeal

Fig.I.1.7. The organiccarbonbudgetof theBlackSeaduringth"elast2000yea$' Top:

so-urcesof organicmattercalculatedas g m-'yr-' Bo!!om:Iale ol organlcmatter'
ALt<tfi4Vooithe total input of organiccarbonis fixed in sedimentsThis valueis
considerablyhigherthaninihe openocean(ModifiedafterDeuser,1971)

than the averageamount of organiccarbon normally fixed inmarine sediments'

the
The main reasJnfor the higherpreservationrate in the Black Seais probably
slower degradationof orginic matter in the absenceof orygen .Up to a certain
The
Doint.a hLh sedimentationrate can alsohelp to preserveorganicmaterial'
matter is hard to
i-por,un.! of thosetwo factorsin the preservationof organic
qr'"riity, *d certainly varies in different environmentsand localities' is
It
obuioui thut in areasiuch as deltas, the high rate of sedimentationis more
important than an anoxic water zone, whictr should be of greater influencein
closed.staenantbodiesof water. As a basisfor comparisonwith the Black Sea'
 andConclusion
Summary 13

the Amazon River dischargesabout 10101organic carbon per year (Williams,

1968).This is about 10Otimes more than the total annualproductionof organic
carbonin the Black Sea.The Amazon River representsapproximately207oof the
total $orldwide river runoff.
Organic maner in q-atersis arbitrarily subdividedinto particulate(living and
deadt arrl "disolr ed" organicmatter (in generalparticles<1p). Approximately
llr-t ..-rithe total organiccarbondischargeof the Amazon River is in a dissolved
sr-:re.rbe rest is panic'ulateorganic matter. Whereas the particulate organic
mener crrrFd inro the seais more significantlocally,the dissolvedorganicmatter
j:Dl : *rler dttribution due to mixing of water masses.No matter what the
:rLrEs!\€-{are that lead to preservationand fossilizationof organicmalter, they
r. J prrme importance for the formation of potential source rocks.

SummaryandConclusion
Photosynthesis is the basisfor massproductionof organicmatter. Abour 2 billion years
ago in the Precambrian,photosynthesisemerged as a worldwide phenornenon.
Herewith the folndation for the food pyramidand the evolutionofhigher forms of life
waslaid. The enrichmentof molecularoxygenin the atmosphereof the earthis a direct
consequence of photosynthesisand the massproductionof organicmatter.
During the earth'shistoryand on a globalscale,the averagepreservationrate ofthe
primary organicproduction,expressedasorganiccarbon,is estimatedto be lessthan
0.l7o. The upper limit of the preservationrate oforganic carbonto be found in certailt
oxygen-deficient environmentsfavorablefor depositionof sourcerock-typesediments
is about47o.