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Introductionto
BiogeochemicalCycles
Chapter4
Allmattercycles...itisneithercreatednor
destroyed...
AstheEarthisessentiallyaclosedsystemwith
respecttomatter,wecansaythatallmatteron
Earthcycles.
Biogeochemicalcycles:themovement(orcycling)
ofmatterthroughasystem

ingeneral...wecansubdividetheEarthsysteminto:
atmosphere
hydrosphere
lithosphere
biosphere
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bymatterwemean:elements(carbon,nitrogen,
oxygen)ormolecules(water)
sothemovementofmatter(forexamplecarbon)
betweenthesepartsofthesystemis,practically
speaking,abiogeochemicalcycle
TheCyclingElements:
macronutrients:requiredinrelativelylargeamounts
"bigsix":carbon
hydrogen
oxygen
nitrogen
phosphorous
sulfur
othermacronutrients:
potassium
calcium
iron
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magnesium
micronutrients:requiredinverysmallamounts,
(butstillnecessary)
boron(greenplants)
copper(someenzymes)
molybdenum(nitrogenfixingbacteria)
GeneralizedBiogeochemicalCycle:

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Biogeochemicalcyclesarepartofthelargercycles
thatdescribethefunctioningofthewholeEarth(not
justthesurfaceparts)
Geologicalcycleconsistsof:
tectoniccycle
rockcycle
hydrologiccycle
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biogeochemicalcycles
Wewillfocusonthehydrologiccycleandthe
biogeochemicalcycles.Thesearethecyclesin
whichhumansinteractthemost.
Hydrologiccycle:introduction
(morelaterwithChapters19and20)

Boxmodel:
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Reservoirs,fluxesandresidencetimes
Reservoirs:km3%
Atmosphere12,700.001
Ocean1,230,000,00097.2
Landsurface
lakes123,000.009
rivers
andstreams1,200.0001
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Landsubsurface
(groundwater)4,000,000.31
Ice(glaciers)28,600,0002.15
Fluxes:km3/yr
P:precipitationtotal496,000
land111,000
ocean385,000
E:evaporationtotal496,000
land71,000
ocean425,000
T:transpirationincludedinevap
(plantevaporation)
R:surfacerunoff26,000
SR:subsurfacerunoff
liquid12,000
ice2,000
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I:infiltration14,000
S:springs2,000
Comparewith
totalhumanuse3,000
Notes:
Moreprecipitationfallsonthelandthan
evaporatesortranspires(40,000km3/yr).
Excessprecipitationleavesasrunoffand
subsurfacerunoff
Lessprecipitationfallsontheoceanthan
evaporatesortranspires(40,000km3/yr).
Oceansexportwatertothelandbythe
atmosphere
humansuse12%ofsurfacerunoff
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Residencetimes:
atmosphereRT=12,700km3
(relativetosumofinfluxes)496,000km3/yr
=0.03yror9days
notethatsinceinfluxesequaloutfluxes,theRT
isthesamerelativetothesumoftheoutfluxes
thisisanimportantRT,asanythingthatis
removedfromtheatmospherebyrainorsnowwill
alsohaveanRTintheatmospherenearlyequalto
this
moreresidencetimes:
Ocean:
RT=1,230,000,000km3(relativetoevap)
425,000km3/yr
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=2,900years
thisappliestothewholeocean(whichcanbe
separatedintothesurfaceanddeepwater)anddoes
notincorporatecirculation
Streamsandrivers:
RT=1,200km3withrespecttooutflow
26,000km3/yr
=.05yror17days
thisistheaverage,butitdoesgiveagoodideaof
thetimethatwaterspendsinriversandstreams
beforeitflowsintotheocean
Groundwater:
RT=4,000,000km3withrespecttooutflow
12,000km3/yr
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=330years
onceagain,thisistheaverage...oldestground
waterscanbe10,000to40,000yearsold...butthis
averagedoestellusthat:
groundwatersaregenerallyoldcomparedwith
humanlifetimes(wetendtoviewthemas"eternal")
groundwatershavelargesizesandlongresidence
times...hardtopollute,butoncepolluted,hardto
cleanup
moreonwaterlaterinChapters19and20...

Introductiontothecarboncycle
Thecarboncycleisoneofthemostimportantto
humansbecauseitisimportanttoourexistence:
oneoftheprimaryelementsforminghuman
tissues
necessarytoplants,thebasisofhumanfood
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andbecauseitisimportanttotheclimatesystem
whichsetsthebackgroundforourenvironment:
carbondioxide(CO2)andmethane(CH4)are
greenhousegaseswhichhelpsetglobal
temperatures
BasicCarboncycle:

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BoxModel:

Reservoirs,FluxesandResidenceTimes
Fluxes:(inbillionsofmetrictons/year)
LandPlants
P:photosynthesis120
PR:plantrespiration60
SR:soilrespiration60
SF:plantstosoils60
FFF:fossilfuelformation0.0001
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FFB:fossilfuelburning6
DEF:deforestation2
Ocean
D:dissolving107
E:exsolving103
CP:carbonateformation4
W:weathering0.6
Volcanoes
V:0.1
Notesonfluxes:
CO2increaseintheatmosphere:
Fluxtotheatmosphere:
Plantrespiration+soilrespiration+fossilfuel
burning+deforestation+oceanexsolving+
weathering...
60+60+6+2+103+0.6=231.6bmt/yr
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Fluxfromtheatmosphere:
Plantphotosynthesis+oceandissolving...
120+107=227bmt/yr
...differenceisbuildupofcarbondioxideinthe
atmosphereofabout4bmt/yr(booksays3...)
Moreonfluxes...
humancausedfluxesaresmall,butpersistent
largestfluxesarebetweenlandplantsand
atmosphere,andtheoceanandtheatmosphere
fluxofcarbonoutoffossilfuels(FFB)is60,000
timesfasterthanfluxintofossilfuels(FFF)
fluxtoatmospherefromFFBandDEF
(6+2bmt/yr)isgreaterthanaccumulationof
carbonintheatmosphere(about4bmt/yr)...thisis
becausetheoceanexchangeworksbydiffusion...
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Fluxbydiffusion=k(CairCocean)
(Cisconcentrationoramount,kisaconstant)

if(CairCocean)goesup,fluxgoesup
if(CairCocean)goesdown,fluxgoesdown
if(CairCocean)reverses,fluxreverses
evenmoreonfluxes...
photosynthesisisthebasisoflifeonEarth...
carbondioxide+water+sunlight_
organicmaterial(sugar)+oxygen
respirationisthereverseofphotosynthesis...
organicmaterial+oxygen=
carbondioxide+water+energy
animalsandplantsrespire,releasingenergyfor
otheractivities...decayisalsoaformofrespiration
Reservoirs:billionsofmetrictons
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Atmosphere:720
Ocean:39,000
Carbonates:100,000,000
Fossilfuels:4,000
Landplants:560
Soils:1500
Notesonreservoirs:
mostcarbonisinrocks(carbonatesandother
sediments)
mostcarbonnotinrocksisintheocean
about3timesmorecarboninsoilsthaninland
plants
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Residencetimes:(years)
(allrelativetosumofoutfluxes)

Landplants~5
atmosphere~3
soils~25
Fossilfuels~650
oceans~350
carbonates~150million
Notesonresidencetimes:
someinfluxesarenotbalancedbyoutfluxes
...theatmosphereandfossilfuels,forexample...so
RT'sareslightlydifferent(andreservoirsare
growing...orshrinking)
theRTofcarbonintheair(mostlycarbondioxide
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,butsomemethane)islongenoughthattheairis
wellmixed(atmospheremixesinabout1year)
theRTofsoilsistheaverageRT...someparts
cycleveryslowly(1,000'sofyears),somepartsvery
rapidly(afewweekstomonths...leaves,for
example)
theRToffossilfuelsreflectsallFF'ssuspectedto
exist...thisisacombinationof:
...recoverable
...unrecoverable(bothphysicallyandeconomically)
RT'sofrecoverableFF's:
coal:~350years
oil:~40years
naturalgas:~60years
Morenotesonresidencetimes:
oceanRTalsoreflectstheaverage,which
combinesthesurfacewater(shortRT,fewmonths
toyears)anddeepwater(longRT,200to400
years)...averageisweightedtowardsdeepwater,as
thisismostofthewater
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oceanRTreflectsthecirculationoftheocean(
deepwaterformation)
Stillmoreonfluxes/residencetimes:
Anthropogenicflux(FFBandDEF)to
atmosphere~8bmt/yr,butatmosphericincreaseis
only~4bmt/yr
Question:Wheredoesthemissing4bmt/yrgo?
Twopossibilities:Photosynthesisvs.Oceanuptake
Importanttoknowthisbecausetheresidence
timesaresodifferent
Carbon=>plantsrecyclesquickly(<70yr)to
atmosphere
Carbon=>oceanrecyclesslowly(>300yr)to
atmosphere

CarbonateSilicateCycle
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Longtermcycleofthecarboncycle,tiedwiththe
rock(silicate)cycle
Timescaleforthiscycleismillionstohundredsof
millionsofyears,sonotamajorconcernof
humans...
Onthistimescale,carboncyclingbyplants,oceans
andtheatmosphereisthoughttobeinbalance(s
teadystateorequilibrium)...socarbondioxide
levelsintheatmospherearethoughttobecontrolled
byweatheringratesandratesofvolcaniceruptions
Weatheringratesarethoughttobecontrolledbyrate
oftectonicuplift...
moreuplift,moreweathering,lessatmospheric
carbondioxide
Mayexplaintheslowdeclineinatmosphericcarbon
dioxidefromlevelsofseveralthousandpartsper
million(ppm)about100millionyearsago,to280
ppminthepreindustrialtime.
Duringthistime,theTibetanPlateauandRocky
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MountainPlateauwereraisedbytectonicactivity...
Alsomayprovidelongtermnegativefeedbackto
keepcarbondioxidelevelsfromgettingtoohigh...
warming_moreevaporation_rain_weathering_
carbonate_removescarbondioxidefrom
atmosphere_cooling

IntroductiontotheNitrogenCycle
Importantcyclebecause:
nitrogenisanecessarynutrient
nitrogenispartofacidrain
TheCycle:

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Someterminology:
LimitingNutrientAmountofanelementnecessary
forplantlifeisinshortsupply
NitrogenFixationChemicalconversionofN2to
morereactiveforms,e.g.
NH3(ammonia)orNO3(nitrate)
DenitrificationChemicalconversionfromnitrate
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(NO3)backtoN2
BoxModel

Reservoirs:(inmillionsofmetrictons)

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Atmosphere:4,000,000,000
LandPlants:3500
Soils:9500
Oceans:23,000,000
SedimentsandRocks:200,000,000,000

NotesonReservoirs:

Buriedsedimentsandrocksarethelargestpoolof
nitrogen,butthisreservoirisaminorpartofthe
cycle.
Lotsofnitrogenintheatmosphere(N2=80%),
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butthisformcan'tbeusedbyplants.
Sonitrogenstillalimitingnutrientneednitrogen
fixationtomakeitusabletoplants.
Fluxes:(inmillionsofmetrictons/year)
Atmospheric
LF:LandFixation140
LD:LandDenitrification130
OF:OceanicFixation50
OD:OceanicDenitrification110
I:IndustrialFixation100
FFB:FossilFuelBurning20
BB:BiomassBurning10
L:Lightning20
Other
D:Decay1200
G:Growth1200
LO:LandtoOcean48
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(Rivers36)
(Dust6)
(NOx6)
OL:OceantoLand15
(SeaSpray)
Burial:10
NotesonFluxes:
Industrialfixationisusedtomakefertilizersto
provideusablenitrogenforcrops.Thisfluxis
comparabletonaturalfixation.
Mostfluxisinlandplantsto/fromsoilsplants
recyclenitrogensinceit'salimitingnutrient.
Specializedbacteriaandlightningaretheonly
naturalwaysthatnitrogenisfixed.
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Lightningmayhavebeennecessaryforlifetobegin:
nolife=>nobacteria=>nobacterialfixation=>no
usablenitrogen=>nolife...
Moreonfluxes:
Howdidagriculturesurvivebeforefertilizers?
Earlycivilizationshadtorelyonnatural
regenerationoffixednitrogen:
Annualfloodsbringfreshsediments(e.g.,Nile
Valley)
Slash/burnagriculture:oncethesoilnutrientsare
depleted,moveontoanewplace
Croprotation:certaincrops(e.g.soybeans)are
goodatfixingnitrogen,others(e.g.corn)useitup
plantonalternateyears

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Nitrogenchemicalcycle

Terminology:
F=fixation,D=denitrification,
O=oxidation

ResidenceTimes
MajorReservoirs:
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Atmosphere:14millionyrs.
Landplants:~3yrs.
Oceans:~20,000yrs.
Soils:~9yrs.
Atmosphericpollutants:
NOx~4days
N2O120yrs.
Notesonresidencetimes:
ReservoirswhereN2isthedominantformof
nitrogen(atmosphere,ocean)havelongresidence
times.

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Reservoirswherefixednitrogenisdominant(
soils,plants)haveshortresidencetimes.
=>N2isverystable,butfixednitrogencompounds
areveryreactive(that'swhyplantscanutilizethem)
e.g.acommonfertilizerisammoniumnitrate,
whichisalsoanexplosive!

N2O,astronggreenhousegas,doesn'tgoaway
quickly!
SourcesofNitrogenPollution:
SMOG
NOxisaproductofautomobileexhaustandother
combustionsources
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=>NO2isthechemicalthatgivessmogit's
characteristicbrowncolor
NO2alsoleadstoozoneproductioninthe
troposphere...
...ozoneisneededinthestratospheretoprotectthe
surfaceoftheearthfromUVradiation,butinthe
troposphereit'sapollutant.
MoreonNitrogenPollution:
AcidRain
NO2intheatmospherecanreacttogivenitricacid:
NO2+OH>HNO3
SO2(sulfurdioxide)alsoreactstoproduceacids.
SO2isoftenaproductfromtheburningofcoal.
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Theseacidsaresolubleinwater:
=>acidrain
Acidrainisaproblemdownwindofmajor
industrialemissions
coalpowerplantsinmidwest=>acidraininthe
easternUS
StillmoreonNitrogenPollution:
Eutrophication=>increasingthenutrientsina
bodyofwater
Mostriversandestuariesarenutrientlimited(either
NorP).Runoffcarryingexcessnitratefertilizers
enrichesthesebodiesofwater.
However:Algaerespondtothisfirst!
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Excessalgae=>depleteallO2inthewater=>other
speciesdie
So:fertilizerrunoffdamagesecosystems.Untreated
sewagealsocausesthisproblem.
ThePhosphorusCycle
Importantbecause:
Phosphorusisanecessary,limitingnutrient
Phosphaterunoffcauseseutrophication
BoxModel:

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Reservoirs:(inmillionsofmetrictons)

Earth'sCrust:20,000,000,000
(recoverable:~20,000)
Ocean:100,000
Freshwater:~100
LandPlants:~3000
Soils:~100,000
Notethatmostofthephosphorusisinrocksthat
areunrecoverable.
Fluxes:(inmillionsofmetrictons/yr)

M:Mining50(humans)
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F:Fertilization50(humans)
W:Weathering10
R:Runoff20
B:Burial13
D:Decay200
G:Growth200
Otherfluxes:
Oceantolandbyseaspray0.03
Oceantolandbyguano0.01
Industrialwastes2
NotesonFluxes:
Phosphoroushasnostablegasphase,soaddition
ofPtolandisslow(lowrainP).
MostPinplantscyclesbetweenlivinganddead
plants...additionbyweatheringissmallcompared
tocyclingwithinplants.
HumanshavegreatlyacceleratedPtransferfrom
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rockstoplantsandsoils(about5xfasterthan
weathering).
NaturaltransferofPfromoceantolandisvery
small...lessthan0.03mmt/yrforseasprayand0.01
mmt/yrforguano.
Sourcesforhumanminingareguanoandveryold
(10to15millionyearsago)rocksformedinshallow
seaswhichdriedup(Florida'sBoneValley).Such
rocksarenotformingtodayasrapidly....
Phosphorousisastronglylimitingnutrient
becauseitcannotbetransferredfromtheoceanto
plantsveryeffectively.
ResidenceTimes:
Ocean:100,000mmt/20mmt/yr=5,000years
(withrespecttoinput).
Availabilitytomarineorganismsislimitedbythe
factthatmostPisinthedeepocean.Main
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productivityareasarenearupwellingzoneswhere
deepwatercomestothesurface.
Landdeposits:
ForphosphaterocksintheU.S.:
2,200mmt/50mmt/yr=44years
Longeriflessconcentrateddepositsaremined
(8,800mmt/50mmt/yr=175years)...majorissue
isminingtechniques(stripminingused)withvisual
impactsandwaterpollution.

ReviewofBasicConcepts
inNutrientCycling

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Notes:
Movementthroughtheatmosphereisgenerally
rapid
Movementthroughthesoilsisgenerallyslow
Movementfromterrestrialbiospheretotheocean
(viastreamflow,usually)mustbereplacedby
movementeitherthroughtheatmosphere(suchas
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withnitrogenandcarbon)orbyweathering(suchas
withphosphorousorcalcium).
Theatmosphericrouteismuchfaster!
Increasedtransportbystreamflowseverelydisrupts
thecyclesofelementswithoutagaseousphase.
ThoughtfortheDay:
Humansclearlydisruptmany,ifnotall
biogeochemicalcycles...andintheprocessthreaten
manyecosystems.
Intheabsenceofhumans,arethebiogeochemical
cyclesstable?
Probablynot...
Lifehasexistedforabout3.5billionyears,anda
completebreakdownhasnotoccurredsinceoxygen
becameavailableabout1.5billionyearsago.
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Changeisapartofnaturalbiogeochemicalcycles
resultinginperiodsofabundantbiotaandperiodsof
scarcebiota(bothoceanandland).

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